Use of metal-free azo _compounds having at least one _6-hydroxypyrid-2-one _coupling component radical and metal _complexes thereof for dyeing _substrates and substrates dyed therewith

ABSTRACT

Metal-free compounds of the formula ##STR1## 1:1 and 1:2 metal complexes thereof, and acid addition salts of metal-free compounds of said formula and 1:1 and 1:2 metal complexes thereof, wherein 
     B is hydrogen; C 1-4  alkyl; C 1-4  alkyl monosubstituted by C 1-4  alkoxy; C 2-4  alkyl substituted by hydroxy; C 5-6  cycloalkyl; C 5-6  cycloalkyl substituted by 1 to 3 C 1-4  alkyl groups; phenyl(C 1-3  alkyl); phenyl(C 1-3  alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from C 1-4  alkyl, C 1-4  alkoxy and halo; --A--NH--R 2  ; --A&#39; 4  --N(R 7 ) 2  ; --A 4  --N.sup.⊕ (R 8 ) 2  R 9  A.sup.⊖  or --N(R 7 ) 2 , 
     R is hydrogen; C 1-4  alkyl; C 5-6  cycloalkyl; C 5-6  cycloalkyl substituted by 1 or 2 C 1-4  alkyl groups; phenyl; phenyl substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy and ethoxy; benzyl; phenylethyl; or benzyl or phenylethyl the phenyl group of which is substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy and ethoxy, 
     R 1  is hydrogen or --N═N--D, wherein D is a diazo component radical, with the proviso that R 1  must be ##STR2## 
      when B is other than --A--NH--R 2 , and 
     T is hydrogen, cyano, --COOR 4 , --CO--N(R 5 )2, --SO 2  --N(R 5 ) 2 , ##STR3## with the provisos that (i) when the compound is a monoazo compound free of sulfo groups, it contains at least one water-solubilizing basic or cationic group, (ii) when the compound is free of sulfo groups and is other than a monoazo compound, it contains at least two water-solubilizing groups, and (iii) when the compound contains one or more sulfo groups, the total number of basic and cationic groups exceeds the number of sulfo groups by at least one, 
     are useful as dyes except for the compounds wherein R 1  is hydrogen which are useful as intermediates.

This application is a division of application Ser. No. 598,236, filedApr. 9, 1984 and now U.S. Pat. No. 4,673,735, which is acontinuation-in-part of application Ser. No. 485,212, filed Apr. 15,1983 and now abandoned.

The invention relates to compounds suitable for use as dyestuffs and tointermediates for making such dyestuffs.

According to the invention there are provided compounds of formula I##STR4## in metal-free or 1:1 or 1:2 metal complex form, and in freeacid or acid addition salt form, in which R is hydrogen; C₁₋₄ alkyl;C₅₋₆ cycloalkyl unsubstituted or substituted by one or two C₁₋₄ alkylgroups; phenyl, benzyl or phenylethyl, the phenyl group of the latterthree substituents being unsubstituted or substituted by one or twogroups selected from methyl, ethyl, methoxy and ethoxy;

T is hydrogen, ##STR5## B is --A--NH--R₂ ; hydrogen; C₁₋₄ alkylunsubstituted or substituted by C₁₋₄ alkoxy; C₂₋₄ alkyl substituted byhydroxy; C₅₋₆ cycloalkyl unsubstituted or substituted by one to threeC₁₋₄ alkyl groups; phenyl (C₁₋₃ alkyl), the phenyl group of which isunsubstituted or substituted by one to three groups selected from C₁₋₄alkyl, C₁₋₄ alkoxy and halogen; --A₄ '--N(R₇)₂ ; --A₄ --N.sup.⊕ (R₈)₂ R₉A.sup.⊖ or --N(R₇)₂ ;

R₁ is a group α ##STR6## or, when B is --A--NH--R₂, hydrogen or--N═N--D; where X_(a) is --O--, --NR₅ -- or --S--;

R₃ is hydrogen, C₁₋₄ alkyl, --N(R₅)₂ or --CON(R₅)₂ ;

R₄ is C₁₋₆ alkyl or phenyl (C₁₋₃ alkyl);

R₅ is hydrogen or C₁₋₄ alkyl; or when two R₅ 's are present attached toa nitrogen atom both R₅ 's together with the N-atom to which they areattached may form a saturated ring which contains one to three heteroatoms;

R₆ is C₁₋₄ alkyl;

A₁ is a residue of a tetrazo component;

R₆₀ is OH and R_(60a) is hydrogen or NH₂ or R₆₀ is NH₂ and R_(60a) isOH;

n is 0, 1 or 2;

A₄ is C₂₋₈ alkylene or C₂₋₈ alkenylene;

A₄ ' is C₁₋₈ alkylene or C₂₋₈ alkenylene;

D is a diazo component radical;

where A is C₂₋₈ alkylene which may be interrupted by up to two heteroatoms; C₂₋₈ alkenylene which may be interrupted by up to two heteroatoms; phenylene or cyclohexylene;

R₂ is ##STR7## q is 0 or 1; R₁₁ is hydrogen, halogen, nitro, C₁₋₄ alkylor C₁₋₄ alkoxy;

R₁₂ is ##STR8## or hydrogen, a is an integer 1 to 3.

R₁₄ is an aliphatic, cycloaliphatic, aromatic or heterocyclic aminegroup in which the N-atom is attached to the triazinyl ring;

R₁₃ is a significance of R₁₄, halogen, --OH, --NH₂, C₁₋₄ alkoxy, phenylor ##STR9## A₂ is a linear or branched C₂₋₆ alkylene or --NH--CO--CH₂ --where the starred N-atom is attached to the --NR₅ group;

Z is --N(R₇)₂ or --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖

each R₇, independently, is hydrogen, C₁₋₆ alkyl, C₂₋₆ alkyl substitutedby an halogen, --OH or --CN group, phenyl(C₁₋₃ alkyl), the phenyl ringof which is unsubstituted or substituted by 1 to 3 groups selected fromhalogen, C₁₋₄ alkyl and C₁₋₄ alkoxy; or C₅₋₆ cycloalkyl unsubstituted orsubstituted by 1 or 3 C₁₋₄ alkyl groups;

or both R₇ 's together with the N-atom to which they are attached form a5- or 6-membered saturated ring which contains one to three hetero atoms(referred to hereafter as the "cyclic significances of R₇ ");

each R₈ independently has one of the non-cyclic significances of R₇except hydrogen and R₉ is C₁₋₄ alkyl unsubstituted or substituted byphenyl or

both R₈ 's, R₉ and the N-atom to which they are attached form apyridinium group (attached by its N-atom) unsubstituted or substitutedby one or two C₁₋₄ alkyl groups; or a 5- or 6-membered saturated ringwhich contains 1 to 3 hetero atoms;

R₁₇ is hydrogen, ##STR10## where X_(o) is a bridging group and A₁₀ has asignificance of A₁ defined above or is a coupling/diazo component

K₁ is a diazo or coupling component;

R₁₉ is hydrogen or when R₁₇ is --N═N--K₁ or --N═N--A₁₀ --N═N--K₁additionally --OH, --NH₂, C₁₋₄ alkyl-carbonylamino, benzoylamino orphenylamino, the phenyl group of the latter two substituents beingunsubstituted or substituted by 1 or 2 substituents selected fromhalogen, --NO₂, --NH₂, C₁₋₄ alkyl and C₁₋₄ alkoxy;

R₂₀ is ##STR11## Q₁ is --CH₂ C.sup.⊕ O--, --N.sup.⊕ HCOCH₂ -- or C₂₋₆alkylene where the starred atom is attached to --NR₅ -- (if present) orthe phenyl ring to which R₂₀ is attached;

Q₂ is --CONHCOCH₂ -- or a significance of Q₁ ;

A.sup.⊖ is a non-chromophoric anion;

with the provisos that:

(i) when the compound of formula I is sulpho-free at least onewater-solubilising basic or cationic group is present if the compound offormula I is a monoazo compound; and at least two water-solubilisinggroups are present if the compound of formula I is other than monoazo;

(ii) when one or more sulpho groups are present in the compound offormula I, the number of cationic and basic groups present is at leastthe number of sulpho groups +1;

(iii) when B is --A--NH--R₂, where A is C₂₋₈ alkylene, R₁ on the samepyridone ring is hydrogen, and T on the same pyridone ring is --CN, thenR₂ on the same pyridone ring is not hydrogen. Preferably in thecompounds of formula I when B is --A--NH--R₂ then group B issulpho-free.

Preferably A₁₀ has only a significance of A₁.

In the specification halogen means fluorine, chlorine, bromine oriodine, preferably chlorine.

For the avoidance of doubt the group D--N═N-- includes the group α.

Where any symbol appears more than once in a formula unless indicated tothe contrary its significances are independent of one another.

Any alkyl, alkylene or alkenylene present is linear or branched unlessindicated otherwise. The alkyl group of any alkoxy group is linear orbranched unless indicated to the contrary.

Any sulpho group present may be in free acid or salt form; when in saltform the --SO₃.sup.⊖ is balanced by a cation M.sup.⊕ (where M.sup.⊕ is anon-chromophoric cation for example Na.sup.⊕, K.sup.⊕ or NH₄.sup.⊕) orby a protonated basic non-cationic group or by a cationic group in themolecule.

Unless otherwise indicated the preferred significance of a variableapplies to that variable regardless of where the variable is set forthin the specification.

Any aliphatic amine group is preferably a mono C₁₋₄ alkyl- or a di-(C₁₋₄alkyl)amino group. Each alkyl group independently may be substituted by1 to 3 substituents independently selected from halogen, phenyl, hydroxyand C₅₋₆ cycloalkyl, but is preferably unsubstituted or monosubstitutedby phenyl or hydroxy, any hydroxy being other than in the α-position.

Any cycloaliphatic amine group present is preferably C₅₋₆cycloalkylamine, the cycloalkyl group of which may be substituted by oneor two C₁₋₂ alkyl groups.

Any aromatic amine group present is preferably aniline, the phenyl ringof which is unsubstituted or substituted by one to three substituentsselected from C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, hydroxy and phenoxy.

Any heterocyclic amino group present (or 5- or 6-membered heterocyclicring) is preferably a pyridine, triazine, pyridazine, pyrimidine, orpyrazine group or a group of the formula ##STR12## (when unsaturated) ora morpholine, pyrrolidine, piperidine, piperazine group (whensaturated). Each group may be substituted by one to three R₆ groups.

R is preferably R' where R' is methyl, ethyl, unsubstituted phenyl,unsubstituted benzyl or unsubstituted cyclohexyl. More preferably R isR" where R" is methyl or unsubstituted phenyl.

T is preferably T' where T' is hydrogen, cyano, ##STR13## or --CON(R₅')₂, where R₃ ' and R₅ ' are defined below. More preferably T is T"where T" is cyano or ##STR14## where R₃ " is defined below. B ispreferably B' where B' is --A'--NH--R₂ ', hydrogen, --CH₃, --C₂ H₅, --C₂H₄ OH, unsubstituted cyclohexyl, benzyl, --(CH₂)₁₋₃ N(R₇ ')₂ or--(CH₂)₂₋₃ N.sup.⊕ (R₈ ')₂ R₉ 'A⊖,

where the symbols are defined below. B is more preferably B" where B" is--A"--NH--R₂ ", hydrogen, --CH₃, --C₂ H₅, benzyl, --(CH₂)_(b) --N.sup.⊕(R₈)₂ R₉ A.sup.⊖,

where the symbols are defined below and b is 2 or 3.

R₁ is preferably R₁ ' where R₁ ' is ##STR15## or when B is --A--NH--R₂,hydrogen or --N═N--D'; and where the symbols are defined below.

Preferably A is A' where A' is C₂₋₈ alkylene or unsubstituted phenylene.More preferably A is A" where A" is 1,2-ethylene, 1,3-propylenepropylene or unsubstituted meta or para phenylene.

Preferably R₂ is R₂ ' where R₂ ' is ##STR16## where the symbols R₁₁ 'and R₁₂ ' are defined below. More preferably R₂ is R₂ " where R₂ " is##STR17## where R₁₂ " is defined below.

Preferably R₃ is R₃ ' where R₃ ' is hydrogen, methyl, ethyl, --NH₂ or--N(CH₃)₂. More preferably R₃ is R₃ " where R₃ " is hydrogen or methyl.

Preferably R₅ is R₅ ' where R₅ ' is hydrogen, methyl or ethyl.Preferably R₅ " is hydrogen or methyl.

Preferably R₆ is R₆ ' where R₆ ' is methyl or ethyl.

Preferably R₇ is R₇ ' where R₇ ' is hydrogen, linear or branched C₁₋₆alkyl, unbranched hydroxyC₂₋₃ alkyl, benzyl, 2-cyanoethyl or both R₇ ''stogether with the N-atom to which they are attached form anunsubstituted pyrrolidine, piperidine, morpholine, piperazine orN-methylpiperazine group.

More preferably R₇ is R₇ " where R₇ " is hydrogen, methyl, ethyl,2-hydroxyethyl or both R₇ "'s together with the N-atom to which they areattached form an unsubstituted morpholine, piperidine, piperazine orN-methylpiperazine group.

Preferably R₈ is R₈ ' where R₈ ' is one of the significances of R₇ 'except hydrogen and R₉ is R₉ ' where R₉ ' is methyl, ethyl, propyl orbenzyl or both R₈ 's and R₉ ' together with the N-atom to which they areattached form a pyridinium ring unsubstituted or substituted by one ortwo methyl groups or a group β ##STR18## where Zo is --O--, a directbond, ##STR19## More preferably R₈ is R₈ " is one of the significancesof R₇ " except hydrogen and R₉ is R₉ " where R₉ " is --CH₃, --C₂ H₅ orbenzyl or both R₈ " and R₉ " together with the N-atom to which they areattached form a pyridinium ring, unsubstituted or substituted by one ortwo methyl groups, or is a group β defined above.

Preferably R₁₁ is R₁₁ ' where R₁₁ ' is hydrogen, chloro, nitro, methylor methoxy.

Preferably R₁₂ is R₁₂ ' where R₁₂ ' is ##STR20## or hydrogen;

More preferably R₁₂ is R₁₂ " where R₁₂ " is hydrogen, --CO--CH₂ --Z" or##STR21## where R₁₃ ", R₁₄ " and Z" are defined below.

Preferably R₁₃ is R₁₃ ' where R₁₃ ' is chloro, --OH, --NH₂, ##STR22##where R₂₁ is unsubstituted C₁₋₁₂ alkyl; C₂₋₁₂ alkyl substituted by --OH;C₃₋₁₂ alkyl interrupted by one to three groups selected from ##STR23##where Y₁ is a C₁₋₈ alkylene or a C₃₋₈ alkenylene group; Z is --N(R₇)₂ or--N.sup.⊕ (R₈)₂ R₉ A.sup.⊖ ;

R₂₃ is halogen, --OH, --NO₂, C₁₋₄ alkyl or C₁₋₄ alkoxy;

R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, a --CO--Y₂ --Z',--NHCO--Y₂ --Z', --CONH--Y₂ --Z', --SO₂ NH--Y₂ --Z', --Y₂ --Z' or--NHNHCOCH₂ --Z',

where Y₂ is C₁₋₈ alkylene.

More preferably R₁₃, is R₁₃ " where R₁₃ " is ##STR24## where R₂₁ ' is##STR25## where R₆ ' is methyl or ethyl, and

Y₂ ' is C₁₋₄ alkylene.

Preferably Z is Z' where Z' is --N(R₇ ')₂ or --N.sup.⊕ (R₈ ')₂ R₉'A.sup.⊖.

More preferably Z is Z" where Z" where Z" is --N(R₇ ')₂ or --N.sup.⊕ (R₈")₂ R₉ "A.sup.⊖.

Preferably R₁₄ is R₁₄ ' where R₁₄ ' is ##STR26## where where R₅ ' andR₂₁ are defined above. More preferably R₁₄ is R₁₄ " where R₁₄ " is##STR27##

Preferably R₁₉ is hydrogen.

Preferably D is D' where D' is ##STR28## where each R₂₆ independently,is hydrogen, halogen, --NO₂, --NH₂, C₁₋₄ alkyl, C₁₋₄ alkoxy, --CN,trifluoromethyl, phenyl, anilino, benzoyl, carbamoyl, phenoxy,halophenoxy, dihalophenoxy, C₁₋₄ alkylsulphonyl, phenylsulphonyl, C₁₋₄alkylsulphonylamino or N,N-di-(C₁₋₄ alkyl)aminosulphonyl;

each R₂₈ independently, is hydrogen, halogen, C₁₋₄ alkyl or C₁₋₄ alkoxyand

X is any one of X₁ to X₆₄ and X₁₀₀ to X₁₀₈ below: X₁ a direct bond, X₂is linear or branched C₁₋₄ alkylene, ##STR29##

More preferably X, when one of R₂₈ is not hydrogen, is a direct bond,X₂, X₁₄, X₂₁, X₃₂ or X₄₀.

Preferably when any phenyl ring to which X is attached is substituted,the substituent is in an ortho position to the azo radical attached tothe said ring.

K_(a) is a diazo or coupling component of the pyrazolone- 5 series,5-aminopyrazole series, α- or β-naphthol series, aniline series, phenolseries, α- or β-amino naphthalene series, aminonaphthol series,acetoacetyl alkyl or arylamide series, barbituric acid or dimedoneseries or diaminopyridine series or is ##STR30##

In the various component series mentioned above the component may besubstituted by such groups as R₁ to R₄₀ hereinbefore or hereinafterdefined.

Preferably K_(a) is K_(a) ' where K_(a) ' is a group of any one of theformulae (a) to (1) below ##STR31##

More preferably D is D" where D" is ##STR32## where each R₂₈independently is hydrogen, halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, X' isdefined above and K_(a) " is defined below.

K_(a) is more preferably K_(a) " where K_(a) " is a group of one of theformulae a₁ to k₁ below: ##STR33## where R₄₆ is hydrogen, ##STR34## eachR₄₇ independently is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, --NO₂or --CN;

R₄₈ is C₁₋₄ alkoxy and each q, independently, is 0 or 1 and R₁₃ ', R₁₄', Y₁ and Z are defined above,

R₃₂ is C₁₋₄ alkyl or phenyl;

each R₃₃ independently is hydrogen, C₁₋₄ alkyl, --(CH₂)₂₋₃ OCH₃,--(CH₂)₂ OH, --(CH₂)₂₋₃ N(CH₃)₂ or --(CH₂)₂₋₃ N.sup.⊕ (CH₃)₃ A.sup.⊖.R₃₃ is preferably R₃₃ ' where R₃₃ ' is hydrogen, --(CH₂)₂ OH, --(CH₂)₃--OCH₃, --(CH₂)₂₋₃ --N(CH₃)₂ or --(CH₂)₂₋₃ N.sup.⊕ (CH₃)₃ A.sup.⊖ ;

R₃₄ is --OH or --NH₂ ;

R₃₅ is C₁₋₄ alkyl, --COOR₆, --CON(R_(5a))₂ or --COHN--Y₁ --Z, whereineach R_(5a) is independently C₁₋₄ alkyl or hydrogen, and R₆ is C₁₋₄alkyl;

R₃₆ is hydrogen, ##STR35## where R₄₉ is hydrogen, ##STR36## each R₅₀independently is hydrogen, halogen, C₁₋₄ alkoxy, --NO₂, --NH₂ or C₁₋₄alkyl;

R₃₇ is ##STR37## R₃₈ is C₁₋₄ alkyl, ##STR38## preferably R₃₈ is R₃₈ ' isR₃₈ ' where R₃₈ ' is --CH₃, --C₂ H₅, --(CH₂)₂ CN or benzyl;

R₃₉ is C₁₋₄ alkyl or --(CH₂)_(m) --Z; preferably R₃₉ is R₃₉ ' where R₃₉' is --CH₃, C₂ H₅ or --(CH₂)_(m') --Z,

R₄₀ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy;

m is an integer 1 to 6 and m is preferably m' where m' is an integerfrom 2 to 4;

k_(b) is a component of formula (a), (b) or (d) to (1) of componentK_(a) ' and K_(b) ' is a component (a₁), (b₁) or (d₁) to (k₁),

Preferably R₂₉ is R₂₉ ' where R₂₉ ' is --(CH₂)_(m') --Z, ##STR39## whereR₄₆ ' is hydrogen, ##STR40## each R₄₇ ' independently is hydrogen,chlorine, bromine, methyl, ethyl, methoxy, ethoxy, --NO₂ or --CN;

R₄₈ ' is methoxy or ethoxy; and

m' is 2, 3 or 4.

Preferably K₁ is K₁ ' where K₁ ' is a group of the formula ##STR41##where R₆₃ and R₆₄ are later defined or has a significance of K_(a) '(independently of K_(a) ').

More preferably K₁ is K₁ " where K₁ " is a group of the formula##STR42## where R₆₃ ' is later defined and R₁₃ ' and R₁₄ ' are definedabove or has a significance of K_(a) " (independently of K_(a) ").

Most preferably K₁ is K_(a) '" where K_(a) '" is a group of the formula##STR43## where the symbols are defined above except R₆₃ " which isdefined below.

Preferably A₁ or A₁₀ is A₁ ' where A₁ ' is ##STR44## where R₅₁ ishydrogen, halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy;

R₅₂ is --OH, halogen, --CN, --CONH₂, --NHCOC₁₋₄ alkyl, --NHCONH₂,--COOH, --SO₃ H, hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy;

each R₅₃ independently is hydrogen, halogen, --CN, C₁₋₄ alkyl, C₁₋₄alkoxy, --COOH, --SO₃ H or --OH;

Yo is a direct bond, --(CH₂)₁₋₃ --, --O--, --S--, --SO₂ --, --NH--CO--,--NH--CONH--, --NHCO--(CH₂)₂₋₃ --CONH--, --CONH(CH₂)₂₋₃ NHCO--,--O--(CH₂)₂₋₃ --O--, --N═N-- or --CH═CH--CO--CH═CH--.

More preferably A₁ or A₁₀ is A₁ " where A₁ " is ##STR45## where R₅₂ ' ishydrogen, chlorine, --OH, methyl or methoxy;

R₅₃ ' is hydrogen, chloro, --CH₃, --OH or --OCH₃ ;

Yo' is a direct bond, --NH--CO-- or --NHCONH--.

Preferably in A₁ " the free bonds shown are in a meta or para positionto each other (in the phenyl ring) or to Y_(o) (in the Y_(o) -containinggroup).

In the compounds of formula I preferably 0 to 4 sulpho groups arepresent, more preferably up to 2 sulpho groups are present.

Preferably X_(o) is X_(o) ' where X_(o) ' is ##STR46## where R₁₃ ' isdefined above.

More preferably X_(o) is X_(o) " where X_(o) " is --NH--,--NHCOCH═CHCONH-- or --NHCO(CH₂)₂ CONH--.

Preferably, R₁₇ is R₁₇ ', where R₁₇ ' is hydrogen, ##STR47## R₂₀ ' is##STR48## and the other symbols are defined above.

More preferably, R₁₇ is R₁₇ " where R₁₇ " is hydrogen, ##STR49## R₂₀ "is ##STR50## and the other symbols are defined above.

Preferably Q₁ is C₂₋₆ alkylene, more preferably C₂₋₃ alkylene, mostpreferably C₃ alkylene.

Preferably R₃₃ is R₃₃ ' where R₃₃ ' is hydrogen, --(CH₂)₂ OH, --(CH₂)₃0CH₃ ; --(CH₂)₂₋₃ --N(CH₃)₂ or --(CH₂)₂₋₃ --N.sup.⊕ (CH₃)₃ A.sup.⊖.

Preferably R₃₆ is R₃₆ ' where R₃₆ ' is hydrogen, ##STR51## where R₄₉ 'is hydrogen, --CO--NH--(CH₂)_(m') --Z', --NHCO(CH₂)₂₋₃ --Z' or ##STR52##each R₅₀ ' independently is hydrogen, chlorine, methyl or methoxy.

Preferably R₃₇ is R₃₇ ' where R₃₇ ' is ##STR53##

Further according to the invention there are provided azo compounds, inmetal-free, 1:1 or 1:2 metal complex form, in free acid or acid additionsalt form of formula II ##STR54## in which B₁ is hydrogen, C₁₋₄ alkyl,C₂₋₄ alkyl substituted by hydroxy, C₅₋₆ cycloalkyl unsubstituted orsubstituted by 1 or 2 methyl groups, phenyl(C₁₋₃ alkyl), --A₄ '--N(R₇)₂,--A₄ --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖ or --N(R₇)₂, and where the other symbolsare defined above.

Preferred compounds of formula II are of formula IIa in metal-free, 1:1or 1:2 metal complex form ##STR55## where B₁ ' is hydrogen, --CH₃, --C₂H₅, --C₂ H₄ OH, cyclohexyl, benzyl, --(CH₂)₂₋₃ --N(R₇ ")₂ or --(CH₂)₂₋₃--N.sup.⊕ (R₈ ")₂ R₉ "A.sup.⊖, and where the other symbols are definedabove.

Preferred compounds of formula IIa are of formula IIa' in metal-free,1:1 or 1:2 metal complex form ##STR56## in which B₁ " is hydrogen,--CH₃, --C₂ H₅, benzyl, --(CH₂)₂₋₃ N(R₇ ")₂ or --(CH₂)₂₋₃ --N.sup.⊕ (R₈")₂ R₉ "A.sup.⊖, where the symbols are defined above.

Alternatively, preferred compounds of formula II are of formula IIb inmetal-free, 1:1 or 1:2 metal complex form ##STR57## where R_(17a) is##STR58## where the symbols are defined above.

Preferred compounds of formula IIb are those in which R_(17a) is R_(17a)' where R_(17a) ' is ##STR59##

Alternatively, preferred compounds of formula I are of formula III inmetal-free, 1:1 or 1:2 metal complex form, in free acid or acid additionsalt form ##STR60## where R₁ ' is hydrogen or --N═--D (more preferably--N═N--D) and the other symbols are as defined above.

Preferred compounds of formula III are of formula IIIa ##STR61## whereR₁ " is hydrogen or --N═N--D' (more preferably --N═N--D') and the othersymbols are defined above. Compounds of formula IIIa are in metal-free,1:1 or 1:2 metal complex form where R₁ " is --N═N--D'.

More preferred compounds of formula III are of formula IIIb ##STR62##where R₁ '" is hydrogen or --N═N--D" and the other symbols are definedabove. Compounds of formula IIIb are in metal-free, 1:1 or 1:2 metalcomplex form when R₁ '" is --N═N--D".

Preferred compounds of formula IIIb are of formula IIIc ##STR63## whereR₁ ^(iv) is hydrogen or --N═N--D'", where D'" is ##STR64## where R₂₆ 'is hydrogen, --NO₂, chloro, methyl, methoxy or chlorophenoxy;

R_(27a) is hydrogen, chloro, methyl or methoxy;

R_(27b) is hydrogen, methyl or methoxy;

each R_(26a) is independently nitro, chloro, methoxy or methyl;

X", when both R_(27a) 's and R_(27b) are hydrogen, is X₁, X₅, X₆, X₇,X₁₀, X₁₁, X₁₂, X₁₆, X₁₇, X₂₂, X₂₅, X₂₆, X₂₇, X₃₀, X₃₁, X₄₉, X₅₀, X₅₁,X₅₂, X₅₃, X₅₄, X₅₈, X₅₉, X₆₄, X₇₀₋₉₀, X₁₀₁ where R₄₃ =--(CH₂)₁₋₂, X₁₀₃(where R₄₃ is --(CH₂)₁₋₂ and R₄₅ is --NH--(CH₂)₂₋₃ --N(C₂ H₅)₂), X₁₀₄(where R₄₄ is hydrogen or g is 2 or 3) and X₁₀₈ (where R₄₃ is --(CH₂)₁₋₂--) and otherwise is X₁, X₄₀, X₇₀, X₇₁, X₈₀, X₈₁, X₈₂ or X₈₅. Compoundsof formula IIIc are in metal-free, 1:1 or 1:2 metal complex form when R₁^(iv) is --N═N--D'".

Preferably when the phenyl rings to which X is attached are substituted,the substituents selected from chloro, methyl and methoxy are in anortho position to the azo group attached to said rings.

Alternatively preferred compounds of formula I are of formula XIV inmetal-free, 1:1 or 1:2 metal complex form; ##STR65## in which one R₆₀ is--OH and the other R₆₀ is --NH₂,

R₆₁ is hydrogen, C₁₋₄ alkoxy or --OH,

R₆₂ is hydrogen, chloro, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy or --OH,

R₆₃ has a significance of R₆₂ independently of R₆₂,

R₆₄ is hydrogen ##STR66## M is hydrogen or a non-chromophoric cation,and the other symbols are defined above,

with the provisos that

(i) the number of cationic and protonatable basic groups exceeds thenumber of sulpho groups present by at least one;

(ii) R₆₄ is in the 3- or 4-position on the phenyl ring to which it isattached (the positions being as indicated).

Preferred compounds of formula XIV are of formula XIV' in metal-free,1:1 or 1:2 metal complex form; ##STR67## in which R₆₁ ' is hydrogen,methoxy or --OH,

R₆₂ ' is hydrogen, chloro or methyl,

R₆₃ ' is hydrogen, methoxy, --OH, methyl or chloro,

and the other symbols are as defined above, with the provisos that

(i) the number of cationic and protonable basic groups present exceedsthe number of sulpho groups present by at least one; and

(ii) the amino group on ring E is in the 3- or 4-position.

More preferred compounds of formula XIV are of formula XIV" inmetal-free, 1:1 or 1:2 metal complex form ##STR68## in which R₆₃ " ishydrogen, --OH or methoxy, and the other symbols are as defined abovewith the provisos that

(i) the number of cationic and protonable basic groups exceeds thenumber of sulpho groups present by at least one;

(ii) the amino group on ring E is in the 3- or 4-position (the positionsbeing as indicated); and

(iii) the azo group on ring G is in the 3- or 4-position (the positionsbeing as indicated).

Preferred metallisable groups are --NH₂, --OH and --O(C₁₋₄ alkyl) whichare situated ortho to an azo bridge on a benzo or a phenyl group.Metallisation of such groups can be represented as follows: ##STR69## inwhich each A₅ independently, is --O-- or --NH-- and

Me_(a) is a 1:1 or 1:2 metal complex forming metal, and both R₆₆ 's andR₆₇ 's are ortho to each other and together form an aromatic ring system(for example together with the two carbon atoms to which they areattached form a ##STR70## group).

Preferred compounds of formula I when in metallised form are of formulaeIVa to IVi: ##STR71## whereY_(a) is --O-- or --NH-- and

Me is copper, chromium, cobalt, nickel, iron, manganese or zinc for 1:1metal complexes (Me is preferably copper in this case) or Me ischromium, cobalt, iron or nickel for 1:2 metal complexes (Me ispreferably iron in this case);

with the provisos that

(i) in the compounds of formulae IVg, IVh and IVi R₆₄ is in the 3- or4-position, the naphthyl azo group on ring G is in the 3- or 4-positionand the number of cationic and protonable basic groups present exceedsthe number of sulpho groups present;

(ii) in the compounds of formula IVh the group --O--Me--O-- is ortho tothe naphthyl azo group; and

(iii) in the compounds of formulae IVh and IVi when Y_(a) is --NH-- thenR₆₀ is --OH, and when Y_(a) is --O-- then R₆₀ is --NH₂.

The entire specification of parent application Ser. No. 06/485,212,filed Apr. 15, 1982 (including claims) is hereby incorporated byreference in its entirety.

Compounds of formula I where R₁ is hydrogen may be prepared by reactinga compound of formula V ##STR72## with a compound of formula V_(a)##STR73## where R_(60a) is halogen and R_(61a) is hydrogen or a group ofthe formula ##STR74## or by reacting a compound of formula V whereR_(61a) is ##STR75## with a compound of formula VI or VII

    NH(R.sub.7).sub.2                                          (VI)

    N(R.sub.8).sub.2 R.sub.9                                   (VII)

Compounds of formula V can be prepared by known methods, for examplewhere R_(61a) is ##STR76## the compound of formula IV can be prepared byreacting a compound of formula VIII ##STR77## where R_(63a) is ##STR78##with a compound of formula IX ##STR79## to form a compound of formula X##STR80## followed by reduction of the nitro group to an amino group orwhere R_(61a) is hydrogen by saponification of the compound of formulaX.

Compounds of formula I where R₁ is ##STR81## can be prepared by couplingto a diazotised compound of formula XI ##STR82## a compound of formulaXIII ##STR83## by known methods.

Compounds of formula I where R₁ is other than hydrogen can be preparedby reacting a diazotised compound of formula XIa or XIIa ##STR84## witha compound of formula XIIIa ##STR85## according to known methods.

Compounds of formula XIV in metal-free form may be prepared by eitherreacting a diazotised compound of formula XV ##STR86## with a compoundof the formula XVI ##STR87## in acid medium to form a compound offormula XVII ##STR88## followed by reacting the compound of formula XVIIwith a diazotised compound of formula XVIII ##STR89## in alkali medium;or by reacting a diazotised compound of formula XVIII with the compoundof formula XVI to form a compound of formula XIX ##STR90## in acidmedium followed by reacting the compound of formula XIX with adiazotised compound of formula XV in alkali medium. The SO₃ H groups canbe converted to the salt form by known methods

Coupling to form compounds of formula I where R₁ is other than hydrogencan be carried out according to known methods. Advantageously, couplingis carried out in aqueous (acid, neutral or alkali) medium at atemperature from -10° C. to room temperature, if necessary in thepresence of a coupling accelerator such as pyridine or urea.Alternatively, coupling may be effected in a mixture of solvents, forexample, water and an organic solvent.

Metallisation of the compounds of formula I when R₁ is other thanhydrogen can be achieved by known methods.

The azo compounds of formula I in 1:1 metal complex form may be preparedby metallising compounds of formula I in metal-free form with a metalselected from copper, cobalt, iron, nickel, manganese, chromium andzinc.

The azo compounds of formula I in 1:2 metal complex form may be preparedby metallising compounds of formula I in metal-free form with a metalselected from chromium, nickel, cobalt and iron.

A further method for the preparation of an azo compound of formula I in1:2 metal complex form is by reacting an azo compound of formula I inmetal-free form with an azo compound 1:1 metal complex when the metal ischromium, nickel, cobalt or iron.

The metallisation process to form a 1:1 metal complex is advantageouslycarried out by treating 1 mole of azo compound with a metallising agentcontaining 1 equivalent of metal.

Metallisation is carried out advantageously in aqueous medium or amixture of water and a water-miscible organic solvent, for exampleacetone, lower alkyl alcohols, dimethylformamide, formamide, glycols oracetic acid at a pH from 1.0 to 8.0, preferably pH 2 to 7. Themetallisation process may be carried out at a temperature from roomtemperature to the boiling point of the reaction medium.

Alternatively, metallisation may be effected in a wholly organic medium(for example dimethylformamide). Advantageously, for instance,cobaltisation may be carried out in the presence of an inorganic nitritesuch as lithium, sodium, ammonium or potassium nitrite in the ratio of 2to 6 moles of nitrite per gram atom of cobalt.

Suitable cobalt-yielding compounds are, for example, cobalt (II) and Co(III) sulphate, acetate, formate or chloride.

Copper-yielding compounds are, for example, cupric sulphate, cupricformate, cupric acetate and cupric chloride.

The nickel-yielding compounds are Ni (II) and Ni (III) compounds, suchas nickel formate, nickel acetate and nickel sulphate.

Preferred manganese-yielding compounds are Mn (II) compounds andiron-yielding compounds are Fe (II) and Fe (III) compounds. Examples ofthese and zinc-yielding compounds are manganese, iron and zinc formate,acetate and sulphate.

Preferred chromium-yielding compounds are Cr (II) and Cr (III) formate,acetate and sulphate.

In the compounds of formula I the anions A.sup.⊖ can be anynon-chromophoric anions such as those conventional in basic dyestuffchemistry. Suitable anions include chloride, bromide, sulphate,bisulphate, methylsulphate, aminosulphonate, perchlorate,benzenesulphonate, oxalate, maleate, acetate, propionate, lactate,succinate, tartrate, malate, methanesulphonate and benzoate, as well ascomplex anions, for example, zinc chloride double salts and anions ofboric acid, citric acid, glycollic acid, diglycollic acid and adipicacid or addition products of orthoboric acid with polyalcohols with atleast one cis diol group present. These anions can be exchanged for eachother by ion exchange resins or by reaction with acids or salts, forexample via the hydroxide or bicarbonate or according to GermanOffenlegungsschrift Nos. 2,001,748 or 2,001,816.

The azo compounds of formula I are suitably worked up into solid orliquid preparations, for example by granulation or by dissolving in asuitable solvent. The compounds of formula I are suitable for dyeing,padding or printing on fibres, threads or textile materials particularlynatural or regenerated cellulose materials for example cotton, orsynthetic polyamides or synthetic polyesters in which the acid groupshave been modified. Such a polyamide is described in Belgian Pat. No.706,104 and such a synthetic polyester is described in U.S. Pat. No.3,379,723.

The azo compounds of formula I may also be applied to bast fibres suchas hemp, flax, sisal, jute, coir or straw.

The azo compounds of formula I are also used for dyeing, padding orprinting fibres, threads or textiles produced therefrom which consist ofor contain homo- or mixed polymers of acrylonitrile or of1,1-dicyanoethylene.

The textile material is dyed, printed or pad-dyed in accordance withknown methods. Acid modified-polyamide is dyed particularlyadvantageously in an aqueous, neutral or acid medium, at temperatures of60° C. to boiling point or at temperatures above 100° C. under pressure.

The textile material may also be dyed by the compounds of formula I inorganic solvents, e.g. in accordance with the directions given in GermanOffenlegungschrift No. 2,437,549.

Cellulose material is mainly dyed by the exhaust process i.e. from along or short bath, at room temperature to boiling temperature,optionally under pressure, whereby the ratio of the bath is from 1:1 to1:100 and preferably from 1:20 to 1:50. If dyeing is effected from ashort bath, then the liquor ratio is 1:5 to 1:15. The pH of the dyebathvaries between 3 and 10 (for short and long dyebaths). Dyeing preferablytakes place in the presence of electrolytes.

Printing may be effected by impregnation with a printing paste producedby known methods.

The dyes of formula I are also suitable for dyeing or printing paper,e.g. for the production of bulk-dyed, sized and unsized paper. Thedyestuffs may similarly be used for dyeing paper by the dipping process.The dyeing of paper is effected by known methods.

The dyes of formula I are also suitable for dyeing or printing leatherby known methods.

Dyeings with good fastness are obtained on both paper and leather.

Dyeings made with the dyes of formula I on leather have good lightfastness properties, good diffusion properties with PVC, good water-,wash and sweat-fastness properties, good fastness to dry cleaning, goodfastness to drops of water and good fastness to hard water.

Dyeings prepared with dyes of formula I (where R₁ is other thanhydrogen) on paper produce a substantially clear spent liquor which isimportant for environmental reasons. The dyes of formula I have goodbuild-up properties, do not run once applied to paper and are not pHsensitive. Dyeings produced with dyes of formula I have good lightfastness and the nuance on exposure for a long time to light fades tonein tone. The dyes of formula I have good wetfastness properties not onlyfor water but also for milk, soap, water, sodium chloride solution,fruit juice, and sweetened mineral water. Further dyeings made with dyesof formula I are fast for alcoholic beverages due to a good alcoholfastness. Further the dyes of formula I have good nuance stability.

The dyes of formula I may be converted into dyeing preparations.Processing into stable liquid or solid dyeing preparations may takeplace in a generally known manner, advantageously by grinding orgranulating or by dissolving in suitable solvents, optionally adding anassistant, e.g. a stabiliser or dissolving intermediary such as urea.Such preparations may be obtained, for example, as described in FrenchPatent Specification Nos. 1,572,030 and 1,581,900 or in accordance withGerman DOS Nos. 2,001,748 and 2,001,816.

Liquid preparations of the compounds of formula I preferably comprise 10to 30% by weight of a compound of formula I and to 30% of a solubilisingagent such as urea, lactic acid or acetic acid, the rest of thecomposition being water. Solid preparations preferably comprise 20 to80% dyestuff, 20 to 80% solubilising agent such as urea or Na₂ SO₄ and 2to 5% water.

In the following Examples all parts and percentages given are by weightand the temperatures given are in degrees Centigrade, unless indicatedto the contrary.

EXAMPLE 1

390 Parts (2 moles) of para-nitrobenzoic acid ethyl ester are warmed in3200 parts of ethanol and 360 parts (6 moles) of ethylene diamine at60°-65°. After stirring for several hours a fine crystalline productresults which after filtration produces 360 parts of a compound offormula (1a) ##STR91## having a melting point (of the unpurifiedproduct) of 132°-134°.

A compound of formula (1b) ##STR92## is formed by reacting the compoundof formula 1a with the product of slight excess pyridine and 1 mole ofchloroacetic acid methyl ester, in ethanol at 55° C.

Without isolating the compound (1b) 1 mole of acetoacetic acid methylester is added to the reaction mixture and this is treated at 25° C. inthe presence of base by known methods to produce a compound of formula(1c) ##STR93## which can be reduced by the Bechamps method to thecorresponding amine.

After adding water to the reaction mixture, the compound of formula (1c)precipitates out.

The compound of forumla (1c) is saponified in 5-7% hydrochloric acidaccording to known methods to form an amine of formula (1d) ##STR94##

The compound of formula 1d is reacted according to known methods inwater at about 90° and a pH of 9 with a compound of formula 1e ##STR95##to form a compound of formula (1f) ##STR96## The compound of formula(1f) is very water soluble, particularly in acid medium and can be usedas a coupling component in the preparation of azo dyestuffs.

EXAMPLE 2

In a similar manner to the method of Example 1, a compound of theformula ##STR97## is formed using 1,3-diaminopropane instead of ethylenediamine and chloroacetyl chloride and trimethylamine instead of thecompound of formula (1e).

EXAMPLE 3

225 Parts (1.5 moles) of m-aminoacetanilide in the form of the acidaddition salt are placed in a mixture of equivoluminar glacial aceticacid and water together with sodium acetate. On cooling to 0°-5° C., 254parts of chloroacetyl chloride (2.25 moles) are added over 2 hours. Aproduct of formula 3a ##STR98## is formed. 1 mole of the compound offormula 3a is reacted according to known methods with 1 mole of pyridineto form a compound of formula 3b ##STR99## Without the need to isolatethe compound of formula 3b 1 mole of acetoacetic acid methyl ester isadded to the reaction mixture and according to known methods at roomtemperature in the presence of base a compound of formula 3c ##STR100##is formed.

At 95°-98° C. the compound of formula 3c is saponified with about 5%hydrochloric acid to form a compound of formula 3d ##STR101##

The compound of formula 3d is converted into that of formula 3e##STR102## in a similar way to that described in Example 1.

EXAMPLES 4 to 12

Compounds of the formula ##STR103## where R is defined in Table 1 below,may be prepared by a method analogous to that of Example 1.

                                      TABLE 1                                     __________________________________________________________________________    Example No.                                                                          R                                                                      __________________________________________________________________________            ##STR104##                                                            5                                                                                     ##STR105##                                                            6                                                                                     ##STR106##                                                            7                                                                                     ##STR107##                                                            8                                                                                     ##STR108##                                                            9                                                                                     ##STR109##                                                            10                                                                                    ##STR110##                                                            11                                                                                    ##STR111##                                                            12                                                                                    ##STR112##                                                            __________________________________________________________________________

EXAMPLES 13 to 44

In the following Examples compounds of the formula ##STR113## where T, Aand R₂ are given in Table 2 below, may be prepared by a method analogousto Example 1. In Table 2, T₂ to T₇ and A₂ to A₃₂ are as given below andA.sup.⊖ is CH₃ COO.sup.⊖ ; ##STR114##

                  TABLE 2                                                         ______________________________________                                        Example No.                                                                             T       A                 R.sub.2                                   ______________________________________                                        13        H       C.sub.2 H.sub.4   H.sub.                                    14        T.sub.2 "                 A.sub.2                                   15        T.sub.3 "                 A.sub.3                                   16        T.sub.4 "                 A.sub.4                                   17        T.sub.6 "                 A.sub.5                                   18        T.sub.7 "                 A.sub.6                                   19        T.sub.4                                                                                                 A.sub.7                                   20        T.sub.4 "                 A.sub.8                                   21        T.sub.5 "                 A.sub.9                                   22        T.sub.4                                                                                ##STR115##       A.sub.10                                  23        T.sub.4 CH.sub.2CHCHCH.sub.2                                                                            A.sub.11                                  24        T.sub.2 "                 A.sub.12                                  25        T.sub.4 C.sub.2 H.sub.4   A.sub.13                                  26        T.sub.4 "                 A.sub.14                                  27        T.sub.4 "                 A.sub.15                                  28        T.sub.4 "                 A.sub.16                                  29        T.sub.4 "                 A.sub.17                                  30        T.sub.4 "                 A.sub.18                                  31        "       "                 A.sub.19                                  32        "       "                 A.sub.20                                  33        "       "                 A.sub.21                                  34        "       "                 A.sub.22                                  35        "       "                 A.sub.23                                  36        "       "                 A.sub.24                                  37        "       "                 A.sub.25                                  38        "       "                 A.sub.26                                  39        "       "                 A.sub.27                                  40        "       "                 A.sub.28                                  41        "       "                 A.sub.29                                  42        T.sub.4 "                 A.sub.30                                  43        "       "                 A.sub.31                                  44        "       "                 A.sub.32                                  ______________________________________                                    

EXAMPLE 45

A compound of formula 45a ##STR116## is prepared by diazotising 1 moleof 4-aminoacetanilide and coupling with 1 mole of the compound If ofExample 1.

By the addition of 30% hydrochloric acid to the aqueous solution ofcompound 45a, a 7% hydrochloric acid containing solution is produced andthis is refluxed for 10 hours. A compound of formula 45b results##STR117## 1 mole of compound 45b is then diazotised and then is coupledto 1 mole of a compound of formula 45c ##STR118## to form a compound offormula 45d ##STR119## and this compound dyes paper a blue violet tone.

A similar product can be obtained by using 1 mole of a compound offormula 45e ##STR120## instead of the compound of formula 45c

EXAMPLE 46

6.9 Parts of 1-amino-4-nitrobenzene (1/20 mole) is diazotised inhydrochloric acid solution at -0° to 5° C. with 3.5 parts (1/20 mole)sodium nitride. Then 1/40 mole of the diazonium solution is coupled to 8parts of 1 amino-8-hydroxynaphthalene-3,6-disulphonic acid (1/40 mole)at pH 1. The remaining 1/40 mole diazonium solution is coupled at pH 9to the monoazo dyestuff so formed to form a compound of formula 46a##STR121##

The nitro groups of the compound 45a are reduced according to knownmethods, then both --NH₂ groups are formed are diazotised and then 1mole of the diazotised compound is coupled to 2 moles the compound Ie ofExample 1 to form a compound of formula 46b. ##STR122##

The compound 46b dyes paper a black tone.

EXAMPLES 47 to 64

Compounds of the formula ##STR123## in which the symbols are defined inTable 3 below (where symbols T₄₋₇ and A₂₋₄ are defined under Examples 13to 44 and the symbols B₂ -B₁₁ are defined below) can be made in ananalogous manner to the method of Example 46. ##STR124##

                                      TABLE 3                                     __________________________________________________________________________    EX.                                                                           No.                                                                              T.sub.a                                                                         R.sub.2                                                                         T.sub.b                                                                         B K.sub.1  K.sub.3  K.sub.2                                          __________________________________________________________________________    47 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                                   ##STR125##                                                                             ##STR126##                                      48 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                          ##STR127##                                                                             ##STR128##                                                                             ##STR129##                                      49 T.sub.4                                                                         H T.sub.5                                                                         B.sub.4                                                                          ##STR130##                                                                             ##STR131##                                                                             ##STR132##                                      50 T.sub.4                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.4                                                                          ##STR133##                                                                             ##STR134##                                                                             ##STR135##                                      51 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                          ##STR136##                                                                             ##STR137##                                                                             ##STR138##                                      52 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                          ##STR139##                                                                             ##STR140##                                                                             ##STR141##                                      53 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                          ##STR142##                                                                             ##STR143##                                                                             ##STR144##                                      54 T.sub.5                                                                         A.sub.2                                                                         T.sub.6                                                                         B.sub.8                                                                          ##STR145##                                                                             ##STR146##                                                                             ##STR147##                                      55 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                          ##STR148##                                                                             ##STR149##                                                                             ##STR150##                                      56 T.sub.7                                                                         A.sub.4                                                                         T.sub.5                                                                         B.sub.8                                                                          ##STR151##                                                                             ##STR152##                                                                             ##STR153##                                      57 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                          ##STR154##                                                                             ##STR155##                                                                             ##STR156##                                      58 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.8                                                                          ##STR157##                                                                             ##STR158##                                                                             ##STR159##                                      59 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                          ##STR160##                                                                             ##STR161##                                                                             ##STR162##                                      60 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                          ##STR163##                                                                             ##STR164##                                                                             ##STR165##                                      61 T.sub.4                                                                         A.sub.2                                                                         T.sub.7                                                                         B.sub.2                                                                          ##STR166##                                                                             ##STR167##                                                                             ##STR168##                                      62 T.sub.5                                                                         A.sub.2                                                                         T.sub.4                                                                         H                                                                                ##STR169##                                                                             ##STR170##                                                                             ##STR171##                                      63 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                          ##STR172##                                                                             ##STR173##                                                                             ##STR174##                                      64 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                          ##STR175##                                                                             ##STR176##                                                                             ##STR177##                                      __________________________________________________________________________

The compounds of Examples 47 to 64 dye paper a black tone.

EXAMPLE 65

1/20 mol of para nitroaniline is diazotised and coupled to 1/20 mol of1-amino-8-hydroxynaphthalene-3,6-disulphonic acid. To the resultingmonoazo dyestuff, 1/20 mol of diazotised1-amino-2-hydroxy-4-nitrobenzene is coupled to give a compound offormula 65a ##STR178##

The nitro groups of the compound 65a are reduced with sodium sulphide atpH 11-12. The diamino disazo compound so formed is tetrazotised as inExample 46 and coupled to 1/10 mol of compound of ie of Example 1 toform a compound of formula 65b ##STR179##

This dyestuff dyes paper a black shade.

This compound may also be metallised with copper, iron, chromium orcobalt to form a 1:1 metal complex or with chromium, cobalt or iron toform a 1:2 metal complex according to known methods.

EXAMPLES 66 to 68

The following compounds can be made by a method analogous to that ofExample 65 (or by other known methods) from the corresponding startingcompounds.

EXAMPLE 66 ##STR180## EXAMPLES 67 and 68

In these Examples the group R_(a) is of the formula ##STR181##

A compound of the formula ##STR182## where R₂ is A₂ (defined underExamples 13 to 44) may be prepared by an analogous method to that ofExample 46 or by any other known method.

A compound of the formula ##STR183## where R₂ is A₂ (defined underExamples 13 to 44) may be prepared by an analogous method to that ofExample 46 (or by any other known method).

In Examples 67 and 68 R₂ may be replaced by hydrogen or any of thegroups A₃ to A₃₂ defined under Examples 13 to 46.

These dyestuffs dye paper a blue tone.

EXAMPLES 69 and 70

In these Examples R_(b) is a group of the formula ##STR184##

A compound of the formula of Example 67 in which R_(a) is replaced byR_(b) (Example 69) can be prepared by an analogous method to that ofExample 67.

A compound of the formula of Example 68 in which R_(a) is replaced byR_(b) (Example 70) may be prepared by an analogous method to that ofExample 68.

In Examples 69 and 70, R₂ may be replaced by hydrogen or any other groupA₃ -A₃₂ defined under Examples 13 to 44. The dyeings produced fromcompounds of Examples 69 and 70 are of a blue tone.

EXAMPLE 71

From the corresponding starting compounds, a compound of the formula 71a##STR185## can be prepared by a method analogous to that of Example 45and from corresponding starting products a compound of formula 71b##STR186## can be prepared by a method analogous to that of Example 45.The compounds of formula 71a and 71b dye paper a blue tone.

EXAMPLE 72

From suitable starting compounds a compound of formula 72a ##STR187##may be prepared by a method analogous to that of Example 45.

A compound of formula 72b ##STR188## where R_(c) is ##STR189## may beformed by diazotising the compound of formula 72a and coupling with acompound of the formula H--R_(c).

The compound of formula 72a is violet in colour and the compound offormula 72b dyes paper a black tone.

EXAMPLES 73 to 106

By an analogous method to that of Example 65 (or by any other knownmethod) compounds of the formula ##STR190## are provided in which thesymbols are defined in the Table 4 below and T₂₋₄ are defined underExamples 13 to 44 and B₄₋₈ are defined under Examples 47 to 64 and B₁₂is ##STR191##

                  TABLE 4                                                         ______________________________________                                                         position                                                                      of     position of                                                            floating                                                                             floating gp.                                          EX.              group in                                                                             in naphtha-                                           No.  T     T.sub.1                                                                             ring A lene ring                                                                             B.sub.1     B                                 ______________________________________                                        73   T.sub.4                                                                             T.sub.4                                                                             4'     3       --(CH.sub.2).sub.3 --N(CH.sub.3).sub.2                                                    B.sub.4                           74   T.sub.4                                                                             T.sub.4                                                                             3'     2       "           B.sub.4                           75   T.sub.4                                                                             T.sub.4                                                                             3'     3       "           B.sub.4                           76   T.sub.4                                                                             T.sub.4                                                                             4'     3       "           H                                 77   T.sub.4                                                                             T.sub.2                                                                             4'     3       "           B.sub.4                           78   T.sub.4                                                                             T.sub.2                                                                             4'     2       "           B.sub.4                           79   T.sub.4                                                                             T.sub.2                                                                             4'     2       "           B.sub.4                           80   T.sub.4                                                                             T.sub.2                                                                             3'     2       "           B.sub.4                           81   T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.8     B.sub.8                           82   T.sub.4                                                                             T.sub.4                                                                             3'     2       B.sub.8     B.sub.8                           83   T.sub.4                                                                             T.sub.4                                                                             3'     3       B.sub.8     B.sub.8                           84   T.sub.4                                                                             T.sub.4                                                                             4'     3       B.sub.8     B.sub.8                           85   T.sub.4                                                                             T.sub.4                                                                             4'     3       B.sub.8     H                                 86   T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.8     H                                 87   T.sub.4                                                                             T.sub.4                                                                             3'     3       B.sub.8     H                                 88   T.sub.4                                                                             T.sub.4                                                                             3'     2       B.sub.8     H                                 89   T.sub.4                                                                             T.sub.4                                                                             4'     3       B.sub.8     B.sub.4                           90   T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.8     B.sub.4                           91   T.sub.4                                                                             T.sub.4                                                                             3'     3       B.sub.8     B.sub.4                           92   T.sub.4                                                                             T.sub.4                                                                             3'     2       B.sub.8     B.sub.4                           93   T.sub.4                                                                             T.sub.2                                                                             4'     3       B.sub.8     B.sub.4                           94   T.sub.4                                                                             T.sub.2                                                                             4'     2       B.sub.8     B.sub.4                           95   T.sub.4                                                                             T.sub.2                                                                             3'     3       B.sub.8     B.sub.4                           96   T.sub.4                                                                             T.sub.2                                                                             3'     2       B.sub.8     B.sub.4                           97   T.sub.2                                                                             T.sub.4                                                                             4'     3       B.sub.4     B.sub.4                           98   T.sub.2                                                                             T.sub.4                                                                             4'     2       B.sub.4     B.sub.8                           99   T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.4     B.sub.8                           100  T.sub.4                                                                             T.sub.4                                                                             4'     3       H           B.sub.8                           101  T.sub.4                                                                             T.sub.4                                                                             4'     2       H           B.sub.8                           102  T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.12    B.sub.8                           103  T.sub.4                                                                             T.sub.4                                                                             4'     3       "           H                                 104  T.sub.4                                                                             T.sub.4                                                                             4'     2       "           B.sub.4                           105  T.sub.4                                                                             T.sub.4                                                                             4'     3       "           B.sub.12                          106  T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.8     B.sub.12                          ______________________________________                                    

The compounds of Examples 73 to 106 may also contain OH groups inpositions 2', 3' or 4'. In these cases these compounds can be metallisedto form 1:1 metal complexes with copper, chromium, cobalt or iron or 1:2metal complexes with chromium, cobalt or iron.

Compounds of Examples 73-106 may also contain OCH₃ groups in positions2', 3' or 4'. In these cases these compounds may be metallised to form1:1 metal complexes, preferably with copper.

The compounds so formed are of the formula ##STR192## or of the formula##STR193## where Me is copper, chromium, cobalt or iron (to form 1:1metal complexes) or chromium, cobalt or iron (to form 1:2 metalcomplexes).

EXAMPLE 107

12.3 Parts of ortho anisidine (0.1 mole) are diazotised and then coupledto a compound of formula 107a ##STR194## to form a compound of theformula 107b ##STR195##

This dyestuff dyes paper a yellow shade. The dyestuff 107b can be usedfor dyeing polyacrylonitrile in the mass.

EXAMPLES 108 to 131

Compounds of the formula ##STR196## in which T, R₂, R_(a) and R_(b) aredefined in Table 5 below and significances T₂₋₇ and A₂₋₄ are definedunder Examples 13 to 44, can be prepared by a method analogous to thatof Example 107.

    ______________________________________                                        Ex.                Significance of R.sub.a and                                                                Significance of R.sub.b and                   No.  T      R.sub.2                                                                              position in phenyl ring                                                                    position in phenyl ring                       ______________________________________                                        108  H      A.sub.2                                                                              H            H                                             109  T.sub.2                                                                              A.sub.3                                                                              3-Cl         H                                             110  T.sub.3                                                                              A.sub.2                                                                              4-Cl         H                                             111  T.sub.4                                                                              H      H            H                                             112  T.sub.4                                                                              H      2-NO.sub.2   H                                             113  T.sub.4                                                                              H      2-NO.sub.2   4-Cl                                          114  T.sub.4                                                                              A.sub.2                                                                              H            H                                             115  T.sub.4                                                                              A.sub.2                                                                              2-NO.sub.2   H                                             116  T.sub.4                                                                              A.sub.2                                                                              2-Cl         4-NO.sub.2                                    117  T.sub.4                                                                              A.sub.2                                                                               ##STR197##  H                                             118  T.sub.4                                                                              A.sub.3                                                                              H            H                                             119  T.sub.4                                                                              A.sub.4                                                                              2-NO.sub.2   4-Cl                                          120  T.sub.4                                                                              A.sub.4                                                                              4-OCH.sub.3  H                                             121  T.sub.5                                                                              H      H            H                                             122  T.sub.5                                                                              A.sub.2                                                                              4-NO.sub.2   H                                             123  T.sub.5                                                                              A.sub.2                                                                              2-Cl         4-NO.sub.2                                    124  T.sub.5                                                                              A.sub.4                                                                               ##STR198##  H                                             125  T.sub.6                                                                              H      H            H                                             126  T.sub.6                                                                              A.sub. 2                                                                             4-NO.sub.2   H                                             127  T.sub.6                                                                              A.sub.4                                                                              2-Cl         4-NO.sub.2                                    128  T.sub.7                                                                              A.sub.2                                                                              2-NO.sub.2   4-Cl                                          129  T.sub.7                                                                              A.sub.4                                                                               ##STR199##  H                                             130  T.sub.4                                                                              A.sub.2                                                                              2-OCH.sub.3  5-CH.sub.3                                    131  T.sub.5                                                                              A.sub.4                                                                              2-OCH.sub.3  5-OCH.sub.3                                   132  T.sub.4                                                                              A.sub.4                                                                              2-CH.sub.3   3-CH.sub.3                                    ______________________________________                                    

The dyestuffs of Examples 108 to 132 produce dyeings of a yellow tone.These dyestuffs are also useful for dyeing polyacrylonitrile in themass.

EXAMPLE 133

Using suitable starting compounds, a compound of formula 133a ##STR200##may be prepared using an analogous method to Example 107.

Dyeings so produced are of a gold-yellow tone.

EXAMPLES 134 to 139

Compounds of the formula ##STR201## in which the symbols are given inTable 6 below may be prepared by known methods from suitable startingcompounds.

                  TABLE 6                                                         ______________________________________                                        EX.                                                                           No.   T     R.sub.2                                                                              R.sub.a R.sub.b R.sub.s                                                                              R.sub.t                             ______________________________________                                        134   T.sub.5                                                                             A.sub.2                                                                              --OCH.sub.3                                                                           --CH.sub.3                                                                            4-CH.sub.3                                                                           H                                   135   T.sub.7                                                                             A.sub.2                                                                              "       --OCH.sub.3                                                                           2-OCH.sub.3                                                                          H                                   136   T.sub.4                                                                             A.sub.4                                                                              "       "       2-CH.sub.3                                                                           5-CH.sub.3                          137   T.sub.6                                                                             A.sub.2                                                                              "       --CH.sub.3                                                                            4-C.sub.4 H.sub.9                                                                    H                                   138   T.sub.5                                                                             A.sub.4                                                                              "       --OCH.sub.3                                                                           2-OCH.sub.3                                                                          5-CH.sub.3                          139   T.sub.4                                                                             A.sub.2                                                                              --CH.sub.3                                                                            --OCH.sub.3                                                                           2-OCH.sub.3                                                                          H                                   ______________________________________                                    

The compounds of Examples 134 to 139 produce dyeings of gold-yellow toorange tones and have good fastness properties.

EXAMPLES 140 to 162

Compounds of the formula ##STR202## in which the symbols are defined inTable 7 below (symbols T₂₋₇ and A₂₋₄ are defined under Examples 13 to 44and symbols B₂₋₁₁ are defined under Examples 47 to 64) may be made byanalogous methods to that of Example 107 from suitable startingcompounds.

                  TABLE 7                                                         ______________________________________                                                               position of                                            EX.                    floating                                               No.      T       R.sub.2                                                                             azo group   T.sub.1                                                                             B                                    ______________________________________                                        140      T.sub.4 A.sub.2                                                                             4           T.sub.4                                                                             B.sub.6                              141      H       A.sub.2                                                                             4           H     H                                    142      T.sub.2 A.sub.2                                                                             4           T.sub.3                                                                             B.sub.2                              143      T.sub.3 A.sub.4                                                                             4           T.sub.4                                                                             B.sub.3                              144      T.sub.4 H     4           H     B.sub.4                              145      T.sub.5 H     4           H     B.sub.5                              146      H       A.sub.2                                                                             4           T.sub.4                                                                             B.sub.6                              147      T.sub.6 A.sub.2                                                                             4           T.sub.2                                                                             B.sub.7                              148      T.sub.7 A.sub.2                                                                             4           H     B.sub.8                              149      H       H     4           T.sub.4                                                                             B.sub.9                              150      H       A.sub.2                                                                             4           H     B.sub.8                              151      H       A.sub.4                                                                             4           H     B.sub.9                              152      T.sub.4 H     3           T.sub.4                                                                             B.sub.6                              153      T.sub.5 H     3           T.sub.5                                                                             B.sub.6                              154      T.sub.4 H     4           T.sub.4                                                                             B.sub.6                              155      T.sub.5 H     3           T.sub.5                                                                             B.sub.6                              156      T.sub.4 A.sub.2                                                                             3           T.sub.5                                                                             H                                    157      T.sub.5 A.sub.4                                                                             3           T.sub.6                                                                             H                                    158      T.sub.3 A.sub.2                                                                             3           T.sub.5                                                                             B.sub.2                              159      T.sub.4 H     4           T.sub.4                                                                             B.sub.10                             160      T.sub.5 A.sub.2                                                                             3           T.sub.4                                                                             B.sub.10                             161      T.sub.4 H     3           T.sub.4                                                                             B.sub.11                             162      T.sub.5 A.sub.2                                                                             4           T.sub.4                                                                             B.sub.11                             ______________________________________                                    

Compounds of Examples 140 to 151, 154, 159 and 162 produce dyeings ofdyeings of a violet tone whereas the compounds of Examples 152, 153, 155to 158, 160 and 161 produce dyeings of a reddish yellow to orange tone.

EXAMPLES 163 to 186

Compounds of the formula ##STR203## in which the symbols are defined inTable 8 below, may be prepared by an analogous method to that of Example107. Symbols T₂₋₄ and A₂₋₄ are defined under Examples 13 to 44 andsymbols K₁₋₁₇ are given below.

Compounds of Examples 163 to 168, 179 and 185 produce dyeings of a redshade, of Examples 169 to 175, 183 and 184 a yellow tone, of Examples176 to 178 a blue tone and of Examples 180 to 182 and 186 an orangetone. ##STR204##

                  TABLE 8                                                         ______________________________________                                        EX.                    Position of floating                                   No.      T       R.sub.2                                                                             azo group      K                                       ______________________________________                                        163      T.sub.4 A.sub.2                                                                             4-             K.sub.1                                 164      T.sub.5 A.sub.2                                                                             4-             K.sub.2                                 165      T.sub.6 A.sub.2                                                                             4-             K.sub.3                                 166      T.sub.4 A.sub.4                                                                             4-             K.sub.4                                 167      T.sub.5 A.sub.4                                                                             4-             K.sub.5                                 168      T.sub.2 A.sub.2                                                                             4-             K.sub.6                                 169      H       A.sub.2                                                                             4-             K.sub.7                                 170      T.sub.4 A.sub.4                                                                             4-             K.sub.8                                 171      H       A.sub.4                                                                             4-             K.sub.9                                 172      T.sub.5 H     4-             K.sub.10                                173      T.sub.5 A.sub.4                                                                             4-             K.sub.11                                174      T.sub.6 A.sub.4                                                                             4-             K.sub.12                                175      T.sub.7 A.sub.2                                                                             4-             K.sub.13                                176      T.sub.4 A.sub.2                                                                             4-             K.sub.14                                177      T.sub.4 A.sub.2                                                                             4-             K.sub.15                                178      T.sub.5 A.sub.4                                                                             4-             K.sub.16                                179      T.sub.6 A.sub.2                                                                             4-             K.sub.17                                180      T.sub.5 A.sub.2                                                                             4-             K.sub.18                                181      T.sub.4 A.sub.2                                                                             3-             K.sub.1                                 182      T.sub.6 H     3-             K.sub.5                                 183      T.sub.7 H     3-             K.sub.8                                 184      T.sub.3 A.sub.4                                                                             3-             K.sub.12                                185      T.sub.4 A.sub.2                                                                             3-             K.sub.14                                186      T.sub.5 H     3-             K.sub.17                                ______________________________________                                    

EXAMPLES 187 to 243

According to a method analogous to that of Example 107 compounds offormula ##STR205## in which the symbols are defined in Table 9 below(where the symbols A₂₋₄ and R₂₋₇ are defined under Examples 13 to 44 andthose symbols of X₁₋₁₀₈ used in Table 9 are defined below) can beprepared.

The symbols X₁ to X₁₀₈ used in Table 9 are as follows: ##STR206##

    __________________________________________________________________________    EX. No.                                                                             T   R.sub.2                                                                           X                                                               __________________________________________________________________________    187   H   A.sub.2                                                                           X.sub.1                                                         188   T.sub.2                                                                           A.sub.2                                                                           X.sub.5                                                         189   T.sub.3                                                                           A.sub.2                                                                           X.sub.6                                                         190   T.sub.4                                                                           A.sub.4                                                                           X.sub.7                                                         191   T.sub.5                                                                           A.sub.4                                                                           X.sub.10                                                        192   T.sub.6                                                                           A.sub.2                                                                           X.sub.11                                                        193   T.sub.7                                                                           A.sub.2                                                                           X.sub.12                                                        194   T.sub.4                                                                           A.sub.2                                                                           X.sub.16                                                        195   H   A.sub.2                                                                           X.sub.17                                                        196   T.sub.4                                                                           A.sub.4                                                                           X.sub.22                                                        197   H   A.sub.2                                                                           X.sub.26                                                        198   T.sub.4                                                                           A.sub.4                                                                           X.sub.27                                                        199   T.sub.5                                                                           H   X.sub.30                                                        200   T.sub.6                                                                           A.sub.2                                                                           X.sub.45                                                        201   T.sub.7                                                                           A.sub.2                                                                           X.sub.49                                                        202   T.sub.4                                                                           A.sub.4                                                                           X.sub.50                                                        203   T.sub.5                                                                           A.sub.2                                                                           X.sub.51                                                        204   T.sub.6                                                                           A.sub.2                                                                           X.sub.52                                                        205   T.sub.7                                                                           A.sub.2                                                                           X.sub.53                                                        206   H   A.sub.2                                                                           X.sub.54                                                        207   T.sub.2                                                                           A.sub.2                                                                           X.sub.58                                                        208   T.sub.4                                                                           A.sub.4                                                                           X.sub.59                                                        209   T.sub.5                                                                           H   X.sub.60                                                        210   T.sub.6                                                                           A.sub.2                                                                           X.sub.61                                                        211   T.sub.7                                                                           A.sub.4                                                                           X.sub.62                                                        212   T.sub.4                                                                           A.sub.2                                                                           X.sub.70                                                        213   H   A.sub.2                                                                           X.sub.71                                                        214   T.sub.2                                                                           A.sub.2                                                                           X.sub.73                                                        215   T.sub.4                                                                           A.sub.2                                                                           X.sub.74                                                        216   T.sub.5                                                                           A.sub.4                                                                           X.sub.75                                                        217   T.sub.6                                                                           A.sub.2                                                                           X.sub.79                                                        218   T.sub.4                                                                           A.sub.4                                                                           X.sub.80                                                        219   T.sub.5                                                                           A.sub.2                                                                           X.sub.81                                                        220   T.sub.4                                                                           A.sub.2                                                                           X.sub.82                                                        221   T.sub.4                                                                           A.sub.2                                                                           X.sub.85                                                        222   T.sub.5                                                                           A.sub.2                                                                           X.sub.86                                                        223   T.sub.6                                                                           H   X.sub.87                                                        224   T.sub.7                                                                           A.sub.3                                                                           X.sub.88                                                        225   T.sub.2                                                                           A.sub.2                                                                           X.sub.89                                                        226   T.sub.3                                                                           A.sub.4                                                                           X.sub.90                                                        227   T.sub.4                                                                           A.sub.2                                                                           X.sub.103 (R.sub.43) = C.sub.2 H.sub.4,                                       R.sub.45 = NH(CH.sub.2).sub.2-3N(C.sub.2 H.sub.5).sub.2)        228   T.sub.5                                                                           A.sub.2                                                                           .sub. X.sub.107                                                 229   H   A.sub.2                                                                           CONH(CH.sub.2).sub.2 CONH(CH.sub.2).sub.2 NHCO                  230   T.sub.2                                                                           A.sub.2                                                                           CONH(CH.sub.2).sub.2 CONH(CH.sub.2).sub.2 NHCO                  231   T.sub.3                                                                           A.sub.2                                                                           CONHC.sub.2 H.sub.4 NHCOOHCHCONHC.sub.2 H.sub.4 NHCO            232   T.sub.4                                                                           A.sub.3                                                                           CONHC.sub.2 H.sub.4 NHCOC.sub.2 H.sub.4 CONHC.sub.2 H.sub.4                   NHCO                                                            233   T.sub.5                                                                           A.sub.4                                                                           .sub. X.sub.107                                                 234   T.sub.5                                                                           A.sub.2                                                             235   T.sub.4                                                                           A.sub.2                                                                            ##STR207##                                                     236   T.sub.4                                                                           H   X.sub.11                                                        237   T.sub.4                                                                           X.sub.85                                                            238   T.sub.4                                                                           H   X.sub.82                                                        239   T.sub.4                                                                           H   X.sub.71                                                        240   T.sub.4                                                                           A.sub.2                                                                           X.sub.11                                                        241   T.sub.4                                                                           A.sub.2                                                                           X.sub.85                                                        242   T.sub.4                                                                           A.sub.2                                                                           X.sub.82                                                        243   T.sub.4                                                                           A.sub.2                                                                           X.sub.71                                                        __________________________________________________________________________

Compounds of Examples 187 and 212 dye paper a red tone; Compounds ofExamples 188 to 190, 194 to 197, 199 to 201, 203 to 211, 214 to 216 and219 to 235, 237, 238, 240 to 243 dye paper a yellow tone; the compoundof Example 191 dyes paper a blue tone and compounds of Examples 192,193, 198, 202, 213, 217 to 218 and 236 to 239 dye paper an orange tone.

EXAMPLE 244

Using suitable starting compounds and a method analogous to that ofExample 107, a compound of the formula ##STR208## may be prepared. Thiscompound dyes paper a red-yellow tone.

EXAMPLES 245 to 258

Compounds of formula ##STR209## in which the symbols are given in Table10 below and symbols A₂₋₄ and T₂₋₇ are given under Examples 13 to 44,B₂₋₁₁ are defined under Examples 47 to 64; K₁₋₁₇ are defined underExamples 163 to 186 and the symbols X₁₋₁₀₈ used in Table 10 are definedunder Examples 187 to 243.

Compounds of Examples 245, 252 and 258 dye paper a red tone, compoundsof Examples 246, 248, and 257 dye paper an orange tone, the compound ofExample 247 dyes paper a blue tone and the compounds of Examples 249 to251 and 253 to 256 dye paper a yellow tone.

                  TABLE 10                                                        ______________________________________                                        EX.                                                                           No.      T        R.sub.2 T.sub.1                                                                              B      X                                     ______________________________________                                        245      H        A.sub.2 T.sub.4                                                                              H      X.sub.1                               246      T.sub.2  A.sub.2 T.sub.5                                                                              B.sub.2                                                                              X.sub.2                               247      T.sub.3  A.sub.3 T.sub.6                                                                              B.sub.3                                                                              X.sub.10                              248      T.sub.4  H       H      B.sub.4                                                                              X.sub.11                              249      T.sub.5  A.sub.2 T.sub.4                                                                              B.sub.6                                                                              X.sub.51                              250      T.sub.6  A.sub.2 T.sub.5                                                                              B.sub.7                                                                              X.sub.53                              251      T.sub.7  A.sub.2 H      B.sub.9                                                                              X.sub.59                              252      T.sub.4  A.sub.4 T.sub.5                                                                              H      X.sub.70                              253      T.sub.5  A.sub.2 H      H      X.sub.81                              254      T.sub.4  A.sub.4 T.sub.2                                                                              B.sub.4                                                                              X.sub.82                              255      T.sub.5  A.sub.2 T.sub.4                                                                              H      X.sub.25                              256      T.sub.4  A.sub.4 T.sub.4                                                                              H      X.sub.86                              257      T.sub.4  A.sub.2 T.sub.4                                                                              B.sub.10                                                                             X.sub.11                              258      T.sub.4  A.sub.2 T.sub.4                                                                              B.sub.11                                                                             X.sub.70                              ______________________________________                                    

EXAMPLES 259 to 268

Compounds of the formula ##STR210## in which the symbols are given inTable 11 below, may be prepared in a manner analogous to that of Example107

    ______________________________________                                        EX.                                                                           No.        T        R.sub.2  X       K                                        ______________________________________                                        259        T.sub.4  A.sub.2  X.sub.1 K.sub.1                                  260        T.sub.5  A.sub.2  X.sub.6 K.sub.4                                  261        H        A.sub.4  X.sub.11                                                                              K.sub.5                                  262        T.sub.4  H        X.sub.18                                                                              K.sub.7                                  263        T.sub.5  A.sub.4  X.sub.55                                                                              K.sub.8                                  264        T.sub.4  A.sub.2  X.sub.59                                                                              K.sub.10                                 265        T.sub.6  A.sub.4  X.sub.70                                                                              K.sub.11                                 266        T.sub.7  A.sub.2  X.sub.82                                                                              K.sub.16                                 267        T.sub.4  A.sub.2  X.sub.85                                                                              K.sub.17                                 268        T.sub.5  A.sub.2  X.sub.11                                                                              K.sub.14                                 ______________________________________                                    

The compound of Example 262 dyes paper a red tone, compounds of Examples259 to 261 dye paper an orange tone and compounds of Examples 262 to 268dye paper a yellow tone.

EXAMPLE 269

Starting with a monoazo compound of formula (269a) ##STR211## andreacting with a cyanuric chloride derivative a compound of formula 269b##STR212## may be formed.

By reacting the compound of formula 269b with the compound of formula269c ##STR213## in water at 90° C. and at pH 9, a compound of formula269d ##STR214## may be formed by a method analogous to that ofExample 1. The compound of Example 269d dyes paper a yellow tone.

EXAMPLE 270

A compound of formula 270a ##STR215## is diazotised and then coupled to2-amino-1,4-dimethylbenzene. The resulting disazo compound is furtherdiazotised and then coupled to a compound of the formula H-K₅ ##STR216##to form a compound of formula 270b ##STR217##

This dyestuff dyes paper a brown tone. Instead of coupling to2-amino-1,4-dimethylbenzene, an equivalent amount of2-methoxy-5-methylaniline will produce a compound of formula 270c##STR218## results.

The compound 270c dyes paper a brown tone.

The compound 270c can be metallised by known methods with such metals ascopper, to form a compound of formula 270d ##STR219## where M_(e) iscopper.

EXAMPLES 271 to 283

Compounds of the formula ##STR220## where the symbols are defined inTable 12 below may be made by a method analogous to that of Example 270and then metallised. Symbols B₂₋₁₁ are given under Examples 47 to 64 andsymbols A₂₋₄ and T₂₋₇ are given under Examples 13 to 44.

The compounds of Examples 271 to 273 and 277 to 281 dye paper a violettone and compounds of Examples 274 to 276 and 282 to 283 dye paper ablue tone.

                  TABLE 12                                                        ______________________________________                                        EX.                                                                           No.  T     R.sub.2                                                                             T.sub.1                                                                           B   X                                                    ______________________________________                                        271  T.sub.5                                                                             A.sub.2                                                                             T.sub.5                                                                           B.sub.8                                                                            ##STR221##                                          272  T.sub.4                                                                             A.sub.4                                                                             T.sub.3                                                                           B.sub.4                                                                            ##STR222##                                          273  T.sub.2                                                                             A.sub.2                                                                             T.sub.6                                                                           B.sub.6                                                                            ##STR223##                                          274  H     A.sub.2                                                                             T.sub.4                                                                           B.sub.8                                                                            ##STR224##                                          275  H     A.sub.2                                                                             T.sub. 5                                                                          H                                                                                  ##STR225##                                          276  T.sub.4                                                                             A.sub.2                                                                             T.sub.7                                                                           B.sub.2                                                                            ##STR226##                                          277  T.sub.4                                                                             H     T.sub.4                                                                           B.sub.6                                                                            ##STR227##                                          278  T.sub.5                                                                             A.sub.2                                                                             T.sub.4                                                                           B.sub.3                                                                            ##STR228##                                          279  T.sub.4                                                                             A.sub.2                                                                             T.sub.4                                                                           B.sub.3                                                                            ##STR229##                                          280  T.sub.4                                                                             A.sub.2                                                                             T.sub.4                                                                           B.sub.8                                                                            ##STR230##                                          281  T.sub.5                                                                             A.sub.4                                                                             T.sub.7                                                                           H                                                                                  ##STR231##                                          282  T.sub.4                                                                             A.sub.2                                                                             T.sub.4                                                                           B.sub.8                                                                            ##STR232##                                          283  T.sub.5                                                                             A.sub.4                                                                             T.sub.7                                                                           H                                                                                  ##STR233##                                          ______________________________________                                    

EXAMPLES 284 to 297

In a similar manner to the method of Example 270, compounds of theformula ##STR234## where the symbols are defined in Table 13 below, canbe prepared. Symbols K₂₋₁₇ are defined under Examples 163 to 186.

The compounds of Examples 284 to 289 and 292 to 295 dye paper a violettone and compounds of Examples 290, 291, 296 and 297 dye paper a bluetone.

                  TABLE 13                                                        ______________________________________                                        EX.                                                                           No.  T     R.sub.2                                                                              K    X                                                      ______________________________________                                        284  T.sub.5                                                                             A.sub.2                                                                              K.sub.5                                                                             ##STR235##                                            285  T.sub.6                                                                             A.sub.4                                                                              K.sub.9                                                                             ##STR236##                                            286  H     H      K.sub.17                                                                            ##STR237##                                            287  T.sub.4                                                                             A.sub.2                                                                              K.sub.3                                                                             ##STR238##                                            288  T.sub.5                                                                             A.sub.2                                                                              K.sub.10                                                                            ##STR239##                                            289  T.sub.6                                                                             A.sub.2                                                                              K.sub.8                                                                             ##STR240##                                            290  T.sub.4                                                                             A.sub.2                                                                              K.sub.4                                                                             ##STR241##                                            291  T.sub.7                                                                             A.sub.4                                                                              K.sub.16                                                                            ##STR242##                                            292  T.sub.4                                                                             A.sub.2                                                                              K.sub.11                                                                            ##STR243##                                            293  T.sub.5                                                                             A.sub.4                                                                              K.sub.14                                                                            ##STR244##                                            294  T.sub.4                                                                             A.sub.2                                                                              K.sub.2                                                                             ##STR245##                                            295  T.sub.4                                                                             A.sub.2                                                                              K.sub.13                                                                            ##STR246##                                            296  T.sub.4                                                                             A.sub.2                                                                              K.sub.10                                                                            ##STR247##                                            297  T.sub.5                                                                             A.sub.2                                                                              K.sub.5                                                                             ##STR248##                                            ______________________________________                                    

EXAMPLES 298 to 300

Compounds of the formula ##STR249## may be formed by diazotising acompound of formula 270a and then coupling with a compound H-K where Kis

The coupling components H-K can be made from known compounds by knownmethods.

EXAMPLE 301

(a) Preparation of a coupling component of formula 301a ##STR250##

91 Parts of cyanuric chloride are suspended in 240 parts of an ice/watermixture. 133 Parts of N,N-diethylaminopropylamine is added dropwise at5° to 10° and the mixture is stirred for 3 hours after which 127 partsof 1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid is added. Thetemperature is raised to 90° and the pH is held at 2.5 to 3 by theportionwise addition of 54 parts of sodium acetate. After 2 hourscondensation is terminated. The solution is allowed to cool whilststirring to 20° where the desired crystalline product deposits. Theproduct is filtered and 265 parts of a grey product results containing217 parts of the coupling component 301a.

(b) Preparation of an amino component of formula 301b ##STR251##

30 Parts of 4-aminoacetanilide are reacted in 500 parts of an ice/watermixture at 0° C. with 50 parts of concentrated hydrochloric acid. Afterthis addition, 55 parts of a 4N sodium nitrite solution is addeddropwise followed by 42 parts of6-hydroxy-4-methyl-3-pyridiniumpyrid-2-one and this mixture is broughtto pH 6 by the addition of sodium carbonate. Coupling occurs immediatelyand an orange dyestuff results. After coupling is completed the compoundis filtered and the resulting press cake is suspended in 300 parts ofwater and then reacted with 100 parts of concentrated hydrochloric acidand heated to 95° C. The splitting off of the acetyl group is completedafter 2 hours. The resulting solution is cooled to room temperature bystirring and the dyestuff of formula 301b falls out as yellow crystals.This is filtered, washed with brine and dried. 170 Parts of a yellowpowder results containing 68 parts of the compound of formula 301b.

(c) Preparation of a compound of formula 301c ##STR252##

20.5 Parts of the compound of formula 301a are suspended in 200 parts ofwater and dissolved therein by the addition of sodium hydroxide.

22.4 Parts of the compound of formula 301b is diazotised by knownmethods and the resulting diazo solution is added dropwise to thecompound of formula 301a, and the pH of the reaction is held at 8 to 9by the addition of sodium hydroxide. Coupling occurs immediately to givea blue dyestuff. After termination of coupling the pH is reduced to 7.5by the dropwise addition of concentrated hydrochloric acid and thedyestuff precipitates completely and then is filtered and dried. Thedyestuff is blue in colour and in the form of its acid addition saltdyes paper a blue colour. The remaining dyebath is colourless. Thewet-fastnesses of the dyeings so produced are good.

EXAMPLE 302

The compound of formula 301c may be prepared by coupling4-aminoacetanilide to the compound of formula 301a, followed bysaponifying in acid medium, diazotising and then coupling to6-hydroxy-4-methyl-3-pyridinium-pyrid-2-one.

EXAMPLE 303

Instead of using 4-aminoaniline in the method of Example 301,p-nitroaniline is used, followed by reducing the nitro group in analkali medium of a sulphuric acid salt. The resulting dyestuff is offormula 301c.

EXAMPLES 304 to 340

Compounds of the formula ##STR253## in which the symbols are defined inTable 14 below, can be prepared by methods analogous to Examples 301 to303.

In these Examples ##STR254##

In group X the starred carbon atom is attached to the azo group attachedto the pyridone.

In column I the numbers 1 to 9 represent the colour of the compound ofthe particular Example.

    ______________________________________                                        1 = orange   2 = bluish-red                                                                              3 = reddish-blue                                   4 = blue     5 = grey-blue 6 = red-violet                                     7 = blue-violet                                                                            8 = violet    9 = brown                                          ______________________________________                                    

The position of groups is given by a figure in parentheses.

    TABLE 14         n and position of   EX. No. R X SO.sub.3 H group R.sub.1a and     position of R.sub.1a group I             304      ##STR255##      ##STR256##      1(3) NHC.sub.3 H.sub.6 N(CH.sub.3).sub.2 (6) 8      305     ##STR257##      ##STR258##      1(3) NHY.sub.1(6) 7      306     ##STR259##      ##STR260##      1(3) NHY.sub.2(6) 7      307     ##STR261##      ##STR262##      1(3) NHY.sub.4(6) 7      308     ##STR263##      ##STR264##      1(3) NHY.sub.1(7) 5      309     ##STR265##      ##STR266##      1(3) NHY.sub.3(7) 5      310     ##STR267##      ##STR268##      1(3)      ##STR269##      6      311     ##STR270##      ##STR271##      2(3;6) NHY.sub.2(8) 4      312     ##STR272##      ##STR273##      2(3;6) NHY.sub.3(8) 4      313     ##STR274##      ##STR275##      2(3;6) NHY.sub.4(8) 4      314     ##STR276##      ##STR277##      1(3) NHY.sub.1(6) 1      315     ##STR278##      ##STR279##      1(3) NHY.sub.2(6) 1      316     ##STR280##      ##STR281##      2(3;6) NHY.sub.1(8) 6      317     ##STR282##      ##STR283##      2(3;6) NHY.sub.3(8) 6      318     ##STR284##      ##STR285##      2(3;6) NHY.sub.1(8) 4      319     ##STR286##      ##STR287##      2(3;6) NHY.sub.2(8) 4      320     ##STR288##      ##STR289##      2(3;6) NHY.sub.1(8) 4      321     ##STR290##      ##STR291##      2(3;6) NHY.sub.1(8) 4      322     ##STR292##      ##STR293##      2(3;6) NHY.sub.1(8) 4      323     ##STR294##      ##STR295##      2(3;6) NHY.sub.1(8) 4      324     ##STR296##      ##STR297##      2(3;6) NHY.sub.1(8) 4      325     ##STR298##      ##STR299##      2(3;6) NHY.sub.2(8) 4      326     ##STR300##      ##STR301##      2(3;6) NHY.sub.1(8) 3      327     ##STR302##      ##STR303##      2(3;6) NHY.sub.1(8) 4      328     ##STR304##      ##STR305##      2(3;6) NHY.sub.2(8) 4      329     ##STR306##      ##STR307##      2(3;6) NHY.sub.1(8) 4      330     ##STR308##      ##STR309##      2(3;6) NHY.sub.1(8) 3      331     ##STR310##      ##STR311##      2(3;6) NHY.sub.1(8) 4      332     ##STR312##      ##STR313##      2(3;6) NHY.sub.2(8) 4      333     ##STR314##      ##STR315##      2(3;6) NHY.sub.1(8) 4      334     ##STR316##      ##STR317##      2(3;6)  NHY.sub.1(8) 4      335     ##STR318##      ##STR319##      2(3;6) NHY.sub.1(8) 4      336     ##STR320##      ##STR321##      2(3;6) NHY.sub.1(8) 9      337     ##STR322##      ##STR323##      2(3;6) NHY.sub.3(8) 9      338     ##STR324##      ##STR325##      2(3;6) NHY.sub.1(8) 4      339     ##STR326##      ##STR327##      1(4) H 2      340     ##STR328##      ##STR329##      0 NHY.sub.1(4) 2

EXAMPLE 341

Starting with a compound of formula 341a ##STR330## a compound offormula 341b ##STR331## can be prepared as follows.

The compound of formula 341a can be made by an analogous method to thatof Example 45.

75 Parts of a compound of formula 341a are diazotised with 3 parts of a4N sodium nitrite solution to which an alkali solution containing 2.5parts of 5,5'-dihydroxy-7,7'-disulpho-2,2'-dinaphthyl urea is addeddropwise. Coupling is fully completed by the addition of 10 parts ofNaOH and a compound of formula 341b results having a blue tone.

EXAMPLES 342 to 340

Compounds of the formula ##STR332## can be prepared by a methodanalogous to that of Example 341 using suitable starting materials. Thesymbols are defined in Table 15 below. In column I the colour numeralsin column I are as for Examples 304 to 340 with additionally10=brownish-red and 11=black.

                                      TABLE 15                                    __________________________________________________________________________    EX. No.                                                                            T         B          K                            I                      __________________________________________________________________________    342                                                                                 ##STR333##                                                                             (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                 ##STR334##                  10                     343                                                                                 ##STR335##                                                                             (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                        ##STR336##                  10                     344                                                                                 ##STR337##                                                                             (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                        ##STR338##                   9                     345                                                                                 ##STR339##                                                                             (CH.sub.2).sub.3 N(CH.sub.3 ).sub.2                                                       ##STR340##                   4                     346                                                                                 ##STR341##                                                                             (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                        ##STR342##                  11                     347  CN                                                                                       ##STR343##                                                                               ##STR344##                  11                     348                                                                                 ##STR345##                                                                              ##STR346##                                                                               ##STR347##                  11                     __________________________________________________________________________

EXAMPLE 349

From appropriate starting compounds, a compound of formula 349a##STR348## can be prepared. The compound 349a dyes paper a grey-violettone.

EXAMPLE 350

10 Parts of the dyestuff of Example 318 are stirred in 200 parts ofwater and warmed to 80°. A solution of 3 parts copper sulphatepentahydrate in 20 parts water and 15 parts of concentrated ammonia ispoured into the dyestuff solution and the temperature is raised to 90°to 95°. After 4 hours metallisation is terminated, 30 parts of NaCl areadded, the mixture is cooled to room temperature and finally 5 parts ofsodium hydroxide are added dropwise.

A dyestuff of formula 350a ##STR349## results. In acid addition saltform compound 350a dyes paper a grey brown tone. The spent liquor ispractically colourless and the wet fastnesses and light fastnesses areexcellent.

EXAMPLE 351

28 Parts of compound 301c powder are dissolved in 90 parts of water and10 parts of lactic acid whilst stirring at 60°. Then the dyestuffsolution is clear-filtered. One obtains 125 parts of a filtrate which isstable to storage for several months and which neither under warm norcold conditions allows the dyestuff to be deposited. This dyestuffsolution may be used directly (or thinned with water) in dyeing paper.

EXAMPLE 352

24 Parts of the compound 301c powder are stirred into 500 parts of waterand then the mixture is acidified with 5 parts of glacial acetic acid.The dyestuff dissolves in solution and then the solution is dried. Acompound of formula 352a ##STR350## results, having in powder form ahigh solubility in cold water.

In Examples 351 and 352 instead of the acids used, such acids ashydrochloric, sulphuric, phosphoric and formic acids may be used andinstead of the dyestuff 301c any of the compounds of Examples 302 to 350may be used.

EXAMPLE 353

80 Parts of the dyestuff of 301c powder are stirred into a solution of20 parts dextrin, 20 parts of glacial acetic acid and 300 parts of waterand a homogeneous suspension suspension results. The mixture is atomisedand a blue granulate results having good handle properties and littledust. Paper can be dyed a blue tone by adding the granulate to a papermass.

In a similar fashion a granulate may be made from any one of compoundsof Examples 1 to 299 and 302 to 350.

EXAMPLE 354

In 600 parts of water 22.2 parts (0.05 mols) of a compound of theformula 354a ##STR351## in hydrochloric acid medium are diazotised with3.45 parts (0.05 mols) of sodium nitrite at 0°-5°. To this solution 15.9parts (0.05 mols) of 1 amino-8-hydroxynaphthalene-3,6 disulphonic acidare added dropwise, dissolved in 150 parts of water and 3 parts ofsodium carbonate. The solution has a pH of 1.5. By the addition of 10parts of sodium acetate over 12 hours the pH is brought to 2.3. Theresulting dyestuff is of formula 354b ##STR352##

22 Parts (0.05 mols) of 2,4bis-(diethylaminopropylamino)-6-(3'-aminophenylamino)-S-triazine inhydrochloric acid medium are diazetised in aqueous medium with 3.45parts (0.05 mols) of sodium nitrite at 0°-5° and are then added to thecompound of formula 354b in acid medium.

By the addition of 45 parts of a 30% aqueous NaOH solution the pH isbrought to 8.5-9. After coupling has finished a dyestuff of the formula354c ##STR353## is obtained. This compound 354c dyes paper and leather ablack tone.

EXAMPLE 355

22 Parts (0.05 mols) of2,4-bis-(diethylaminopropylamino)-6-(3'-aminophenylamino)-3-triazine inhydrochloric acid medium are diazotised in aqueous medium with 3.45parts (0.05 mols) of sodium nitrite at 0°-5°. This is then added in acidmedium to 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid and then22.2 parts of the compound of formula 354a (from Example 354) are addedin alkali medium to produce the compound of formula 355a ##STR354##

This is an isomeric form of the compound 354c and also dyes paper andleather a black tone.

Both dyes 354c and 355a have good fastness properties.

EXAMPLES 356-380

Compounds of the formula ##STR355## in which the symbols are defined inTable 16 can be formed by a method analogous to that of Example 354 orExample 355 from appropriate starting materials. In these Examples thesymbols A₃₃₋₄₂ are as defined below. ##STR356##

                                      TABLE 1b                                    __________________________________________________________________________            Positions                                                                          Position                                                                 and sig-                                                                           of --N═N     Position and                                    Ex.     nificance                                                                          on ring          significance                                    No.                                                                              T B  of R.sub.62                                                                        G      R.sub.60a                                                                        R.sub.60b                                                                        R.sub.63                                                                          of R.sub.64                                     __________________________________________________________________________    356                                                                              T.sub.4                                                                         A.sub.33                                                                         H    4      OH NH.sub.2                                                                         H   4-A.sub.38                                      357                                                                              T.sub.4                                                                         "  H    4      NH.sub.2                                                                         OH H   4-A.sub.38                                      358                                                                              T.sub.4                                                                         "  H    3      OH NH.sub.2                                                                         H   3-A.sub.38                                      359                                                                              T.sub.4                                                                         "  H    3      NH.sub.2                                                                         OH H   3-A.sub.38                                      360                                                                              T.sub.4                                                                         "  H    3      OH NH.sub.2                                                                         H   4-A.sub.38                                      361                                                                              T.sub.4                                                                         "  H    3      NH.sub.2                                                                         OH H   4-A.sub.38                                      362                                                                              T.sub.2                                                                         A.sub.35                                                                         H    4      OH NH.sub.2                                                                         H   3-A.sub.38                                      363                                                                              T.sub.5                                                                         "  H    4      OH NH.sub.2                                                                         H   3-A.sub.38                                      364                                                                              T.sub.4                                                                         A.sub.34                                                                         H    4      OH NH.sub.2                                                                         H   3-A.sub.38                                      365                                                                              T.sub.4                                                                         A.sub.35                                                                         H    4      OH NH.sub.2                                                                         H   3-A.sub. 38                                     366                                                                              T.sub.4                                                                         A.sub.36                                                                         H    4      OH NH.sub.2                                                                         H   3-A.sub.38                                      367                                                                              T.sub.4                                                                         A.sub.37                                                                         H    4      OH NH.sub.2                                                                         H   3-A.sub.38                                      368                                                                              T.sub.4                                                                         A.sub.35                                                                         H    4      OH NH.sub.2                                                                         H   3-A.sub.39                                      369                                                                              T.sub.4                                                                         "  H    4      OH NH.sub.2                                                                         H   3-A.sub.40                                      370                                                                              T.sub.4                                                                         "  H    4      OH NH.sub.2                                                                         H   3-A.sub.41                                      371                                                                              T.sub.4                                                                         "  H    4      OH NH.sub.2                                                                         H   3-A.sub.42                                      372                                                                              T.sub.4                                                                         A.sub.33                                                                         OH(4)                                                                              3      OH NH.sub.2                                                                         H   3-A.sub.38                                      373                                                                              T.sub.4                                                                         "  OH(4)                                                                              3      OH NH.sub.2                                                                         H   3-A.sub.38                                      374                                                                              T.sub.4                                                                         "  OH(3)                                                                              4      OH NH.sub.2                                                                         H   3-A.sub.38                                      375                                                                              T.sub.4                                                                         "  OH(3)                                                                              4      OH NH.sub.2                                                                         H   3-A.sub.38                                      376                                                                              T.sub.4                                                                         A.sub.35                                                                         H    4      NH.sub.2                                                                         OH OH  3-A.sub.42                                      377                                                                              T.sub.4                                                                         "  H    4      NH.sub.2                                                                         OH OH  3-A.sub.42                                      378                                                                              T.sub.4                                                                         "  H    4      NH.sub.2                                                                         OH OCH.sub.3                                                                         3-A.sub.42                                      __________________________________________________________________________

APPLICATION EXAMPLE A

70 Parts of chemically bleached sulphite cellulose obtained frompinewood and 30 parts of chemically bleached sulphite cellulose obtainedfrom birchwood are ground in 2000 parts of water in a Hollander. 0.5Parts of the dyestuff from Example 301 of formula 301c (as an acidaddition salt, e.g. Example 351) are sprinkled into this pulp. Paper isproduced from this pulp after mixing for 20 minutes. The absorbent paperwhich is obtained in this manner is dyed in a blue tone. The waste wateris practically colourless.

APPLICATION EXAMPLE B

0.5 Parts of the dyestuff from Example 301 of formula 301c (as an acidaddition salt, e.g. Example 351) are added to 100 parts of chemicallybleached sulphite cellulose which have been ground in a Hollander with200 parts of water. Sizing takes place after thorough mixing for 15minutes. The paper which is produced from this material has a blue toneand good light- and wet-fastnesses.

APPLICATION EXAMPLE C

An absorbent length of unsized paper is drawn at 40° to 50° C. through adyestuff solution having the following composition:

0.5 parts of the dyestuff from Example 314 (as an acid addition salt)

0.5 parts of starch and

99.0 parts of water.

The excess dyestuff solution is squeezed out through two rollers. Thedried length of paper is dyed in an orange tone.

APPLICATION EXAMPLE D

100 Parts freshly tanned and neutralised chrome leather are agitated for30 minutes in a vessel with a dyebath of 250 parts water at 55° C. and0.5 parts of the dyestuff of Examples 346 in acid addition salt form,and then treated in the same bath for 30 minutes with 2 parts of ananionic fatty liquor based on sulphonated train oil. The leather is thendried and prepared in the normal way, giving a leather evenly dyed in ablack tone.

Other low affinity vegetable-tanned leathers can similarly be dyed byknown methods.

APPLICATION EXAMPLE E

2 Parts of the dyestuff of Example 350 in acid addition salt form aredissolved in 4000 parts demineralised water at 40° C. 100 Parts of apre-wetted cotton textile substrate are added, and the bath is raised toboiling point over 30 minutes and held at the boil for 1 hour. Afterrinsing and drying, a greyish-blue dyeing is obtained having good light-and wet-fastnesses. The dye exhausts practically totally, and the wastewater is almost colourless.

The dyestuffs of any of the other Examples may be used in place of thecompound of the particular Example named in any one of ApplicationExamples A to C (if Examples 301 to 353 then in acid addition saltform). The dyes so used may be in the form of solid or liquidpreparations.

What is claimed is:
 1. A process for dyeing or printing a substratecomprising applying a dye to a substrate, said dye being a metal-freecompound of the formula ##STR357## or a 1:1 or 1:2 metal complexthereof, or an acid addition salt of a metal-free compound of saidformula or a 1:1 or 1:2 metal complex thereof, wherein B is hydrogen;C₁₋₄ alkyl; C₁₋₄ alkyl monosubstituted by C₁₋₄ alkoxy; C₂₋₄ alkylsubstituted by hydroxy; C₅₋₆ cycloalkyl; C₅₋₆ cycloalkyl substituted by1 to 3 C₁₋₄ alkyl groups; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) thephenyl group of which is substituted by 1 to 3 substituents selectedfrom C₁₋₄ alkyl, C₁₋₄ alkoxy and halo; --A--NH--R₂ ; --A₄ '--N(R₇)₂ ;--A₄ --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖ or --N(R₇)₂,wherein A is linear orbranched C₂₋₈ alkylene; linear or branched C₂₋₈ alkylene interrupted by1 or 2 hetero atoms; linear or branched C₂₋₈ alkylene; linear orbranched C₂₋₈ alkenylene interrupted by 1 or 2 hetero atoms; phenyleneor cyclohexylene, A₄ is linear or branched C₂₋₈ alkylene or linear orbranched C₂₋₈ alkenylene, A₄ ' is linear or branched C₁₋₈ alkylene orlinear or branched C₂₋₈ alkenylene, and R₂ is ##STR358## wherein R₁₁ ishydrogen, halo, nitro, C₁₋₄ alkyl or C₁₋₄ alkoxy, and R₁₂ is--CO--(CH₂)_(a) --Z or ##STR359## wherein Z is --N(R₇)₂ or --N.sup.⊕(R₈)₂ R₉ A.sup.⊖, and a is 1, 2 or 3, R is hydrogen; C₁₋₄ alkyl; C₅₋₆cycloalkyl; C₅₋₆ cycloalkyl substituted by 1 or 2 C₁₋₄ alkyl groups;phenyl; phenyl substituted by 1 or 2 substituents selected from methyl,ethyl, methoxy and ethoxy; benzyl; phenylethyl; or benzyl or phenylethylthe phenyl group of which is substituted by 1 or 2 substituents selectedfrom methyl, ethyl, methoxy and ethoxy, R₁ is --N═N--D, wherein D is adiazo component radical, with the proviso that R₁ must be ##STR360##when B is other than --A--NH--R₂, wherein A₁ is a tetrazo componentradical, R₁₇ is hydrogen, --N═N--K₁, --N═N--A₁₀ --N═N--K₁, ##STR361##wherein A₁₀ is a tetrazo component radical or a coupling/diazo componentradical, K₁ is a diazo component radical or a coupling componentradical, R₂₀ is --(NR₅)_(q) --Q₁ --N(R₇)₂, --(NR₅)_(q) --Q₂ --N.sup.⊕(R₈)₂ R₉ A.sup.⊖ or ##STR362## wherein Q₁ is linear or branched C₂₋₆alkylene, --CH₂ C^(*) O-- or --CH₂ CON^(*) H--, wherein the * denotesthe atom attached to the --(NR₅)_(q) -- radical, and Q₂ is linear orbranched C₂₋₆ alkylene, --CH₂ C^(*) O--, --CH₂ CON^(*) H-- or --CH₂CONHC^(*) O--, wherein the * denotes the atom attached to the--(NR₅)_(q) -- radical, X_(o) is a bridging radical, R₁₉ is hydrogen;hydroxy; amino; (C₁₋₄ alkyl)carbonylamino; benzoylamino; phenylamino; orbenzoylamino or phenylamino the phenyl group of which is substituted by1 or 2 substituents selected from halo, nitro, amino, C₁₋₄ alkyl andC₁₋₄ alkoxy, with the proviso that R₁₉ must be hydrogen when R₁₇ isother than --N═N--K₁ and --N═N--A₁₀ --N═N--K₁, and R₆₀ is hydroxy oramino, and R_(60a) is hydrogen, hydroxy or amino, with the proviso thatR_(60a) is hydrogen or amino when R₆₀ is hydroxy and is hydroxy when R₆₀is amino, and T is hydrogen, cyano, --COOR₄, --CO--N(R₅)₂, --SO₂--N(R₅)₂, ##STR363## wherein each R₃ is independently hydrogen, C₁₋₄alkyl, --N(R₅)₂ or --CO--N(R₅)₂, R₄ is C₁₋₆ alkyl or phenyl(C₁₋₃ alkyl),R₆ is C₁₋₄ alkyl, and X_(a) is --O--, --NR₅ -- or --S--,wherein each R₅is independently hydrogen or C₁₋₄ alkyl or, when two R₅ 's are attachedto a nitrogen atom, both R₅ 's taken together and with the nitrogen atommay form a saturated ring containing 1 to 3 hetero atoms, each R₇ isindependently hydrogen; C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by halo,hydroxy or cyano; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenylgroup of which is substituted by 1 to 3 substituents selected from halo,C₁₋₄ alkyl and C₁₋₄ alkoxy; C₅₋₆ cycloalkyl or C₅₋₆ cycloalkylsubstituted by 1 or 3 C₁₋₄ alkyl groups, or both R₇ 's taken togetherand with the nitrogen atom to which they are attached form a 5- or6-membered saturated ring containing 1 to 3 hetero atoms, each R₈ isindependently C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by halo, hydroxy orcyano; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenyl group of whichis substituted by 1 to 3 substituents selected from halo, C₁₋₄ alkyl andC₁₋₄ alkoxy; C₅₋₆ cycloalkyl or C₅₋₆ cycloalkyl substituted by 1 or 3C₁₋₄ alkyl groups, each R₉ is independently C₁₋₄ alkyl or C₁₋₄ alkylsubstituted by phenyl or both R₈ 's and R₉ taken together and with thenitrogen atom to which they are attached are pyridinium; pyridiniumsubstituted by 1 or 2 C₁₋₄ alkyl groups; or a 5- or 6-membered saturatedring containing 1 to 3 hetero atoms, each R₁₃ is independently amino; analiphatic, cycloaliphatic, aromatic or heterocyclic amino group thenitrogen atom of which is attached to the 1,3,5-triazine ring; halo;hydroxy; C₁₋₄ alkoxy; phenyl or ##STR364## wherein A₂ is linear orbranched C₂₋₆ alkylene or --N^(*) HCOCH₂ --, wherein the * denotes theatom attached to the --NR₅ -- radical, and R, R₁, R₅ and T are asdefined above, each R₁₄ is independently an aliphatic, cycloaliphatic,aromatic or heterocyclic amino group the nitrogen atom of which isattached to the 1,3,5-triazine ring, each n is independently 0, 1 or 2,each q is independently 0 or 1, and each A.sup.⊖ is independently anon-chromophoric anion, with the provisos that (i) when the compound ofFormula I is a monoazo compound free of sulfo groups, it contains atleast one water-solubilizing basic or cationic group, (ii) when thecompound of Formula I is free of sulfo groups and is other than amonoazo compound, it contains at least two water-solubilizing groups,and (iii) when the compound of Formula I contains one or more sulfogroups, the total number of basic and cationic groups exceeds the numberof sulfo groups by at least one.
 2. A process according to claim 1wherein the substrate is a fiber, thread or textile material comprisinga natural or regenerated cellulosic material or a homopolymer orcopolymer of acrylonitrile or 1,1-dicyanoethylene or is leather orpaper.
 3. A process according to claim 1 wherein T is hydrogen, cyano,##STR365## wherein each R₃ ' is independently hydrogen, methyl, ethyl,amino or dimethylamino, andeach R₅ ' is independently hydrogen, methylor ethyl.
 4. A process according to claim 1 wherein B is hydrogen,methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂,--(CH₂)_(b) --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖ or --A'--NH--R₂ ', whereinA'is linear or branched C₂₋₈ alkylene or phenylene, R₂ ' is ##STR366##wherein R₁₁ ' is hydrogen, chloro, nitro, methyl or methoxy, R₁₂ ' is##STR367## wherein R₁₃ ' is chloro, hydroxy, amino, N,N-di-(C₂₋₄hydroxyalkyl)amino, ##STR368## wherein R₁₁ ' is as defined above, R₁₄ 'is ##STR369## Z' is --N(R₇ ')₂ or --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, whereinR₇ ', R₈ ' and R₉ ' are as defined below, and t is 1 or 2, and q is 0 or1, each R₇ ' is independently hydrogen, C₁₋₆ alkyl, n-hydroxy(C₂₋₃alkyl), benzyl or 2-cyanoethyl or --N(R₇ ')₂ is pyrrolidino, piperidino,morpholino, piperazino or N'-methylpiperazino, each R₈ ' isindependently C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl,and R₉ ' is methyl, ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ ' ispyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR370##wherein Zo is a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂ --,--NH--, --NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖, and R₉ ' is as definedabove, a is 1, 2 or 3, and b is 2 or 3,wherein R₅ ' is hydrogen, methylor ethyl, and R₂₁ is C₁₋₁₂ alkyl; C₂₋₁₂ alkyl substituted by hydroxy;C₃₋₁₂ alkyl interrupted by 1 to 3 radicals selected from --NR₇ -- and--N.sup.⊕ (R₈)₂ --A.sup.⊖ ; --NHCO--CH₂ --Z; --CH₂ --CONH--Y₁ --Z; --Y₁--Z; ##STR371## wherein R₂₃ is halo, hydroxy, nitro, C₁₋₄ alkyl or C₁₋₄alkoxy, R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, --CO--Y₂ --Z',--NHCO--Y₂ --Z', --CONH--Y₂ --Z'--SO₂ NH--Y₂ --Z', --Y₂ --Z' or--NHNHCO--CH₂ --Z',wherein Y₂ is linear or branched C₁₋₈ alkylene, andR₇ ', R₈ ', R₉ ' and Z' are as defined above, each Y₁ is independentlylinear or branched C₁₋₈ alkylene or linear or branched C₃₋₈ alkenylene,and Z' is as defined above,wherein each R_(5a) is independently hydrogenor C₁₋₄ alkyl, each R₆ is independently C₁₋₄ alkyl, and each A.sup.⊖ isindependently a non-chromophoric anion.
 5. A process according to claim1 wherein R is methyl, ethyl, phenyl, benzyl or cyclohexyl.
 6. A processaccording to claim 1 wherein R₁ is --N═N--D', wherein D' is ##STR372##with the proviso that D' must be ##STR373## when B is other than--A--NH--R₂, wherein A₁ ' is ##STR374## wherein R₅₁ is hydrogen, halo,C₁₋₄ alkyl or C₁₋₄ alkoxy,R₅₂ is hydrogen, hydroxy, halo, cyano,--CONH₂, (C₁₋₄ alkyl)carbonylamino, --NHCONH₂, carboxy, sulfo, C₁₋₄alkyl or C₁₋₄ alkoxy, each R₅₃ is independently hydrogen, halo, cyano,C₁₋₄ alkyl, C₁₋₄ alkoxy, carboxy, sulfo or hydroxy, and Yo is a directbond, --(CH₂)_(a) --, --O--, --S--, --SO₂ --, --NHCO--, --NHCONH--,--NHCO--(CH₂)_(b) --CONH--, --CONH--(CH₂)_(b) --NHCO--, --O--(CH₂)_(b)--O--, --N═N-- or --CH═CH--CO--CH═CH--,K_(a) ' is ##STR375## wherein R'is methyl, ethyl, phenyl, benzyl or cyclohexyl, each R₂₈ isindependently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₂₉ is--(CH₂)_(m) --Z, ##STR376## wherein R₄₆ is hydrogen, ##STR377## each R₄₇is independently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro orcyano, and R₄₈ is a C₁₋₄ alkoxy, R₃₂ is C₁₋₄ alkyl or phenyl, each R₃₃is independently hydrogen, C₁₋₄ alkyl, --(CH₂)_(b) --OCH₃,2-hydroxyethyl, --(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b) --N.sup.⊕ (CH₃)₃A.sup.⊖, R₃₄ is amino or hydroxy, R₃₅ is C₁₋₄ alkyl, --COOR₆,--CO--N(R_(5a))₂ or --CONH--Y₁ --Z, R₃₆ is hydrogen, ##STR378## whereinR₄₉ is hydrogen, --CONH--Y₁ --Z, --SO₂ NH--Y₁ --Z, --NHCO--(CH₂)_(b)--Zor ##STR379## and each R₅₀ is independently hydrogen, halo, C₁₋₄alkoxy, C₁₋₄ alkyl, nitro or amino, R₃₇ is hydrogen, --NHCO--(CH₂)_(a)--Z, --SO₂ NH--Y₁ --Z, --CONH--Y₁ --Z, --CONHNH₂, --NH--Y₁ --Z, --CH₂--Z, --NHNHCO--CH₂ --Z, nitrophenylcarbamoyl or ##STR380## R₃₈ is C₁₋₄alkyl, benzyl or 2-cyanoethyl, R₃₉ is C₁₋₄ alkyl or --(CH₂)_(m) --Z,each R₄₀ is independently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, and T' ishydrogen, cyano, ##STR381## wherein each R₃ ' is independently hydrogen,methyl, ethyl, amino or dimethylamino, R₁₇ ' is hydrogen, ##STR382##wherein K₁ ' is ##STR383## wherein R₆₃ is hydrogen, chloro, nitro, C₁₋₄alkyl, C₁₋₄ alkoxy or hydroxy, R₆₄ is hydrogen, dimethylamino,trimethylammonium A.sup.⊖, diethylamino, triethylammonium A.sup.⊖,--CO--Y₂ --Z, --CONH--Y₂ --Z, --Y₂ --Z, --NHCO--Y₂ --Z, --SO₂ NH--Y₂--Z, --NHNHCO--CH₂ --Z or ##STR384## and K_(b), R', R₂₈, R₂₉, R₃₂, R₃₃,R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉, R₄₀ and T' are as defined above, and R₂₀ 'is ##STR385## X_(o) ' is --NH--, --NHCONH--, --NHCO--CH═CH--CONH--,--NHCO--(CH₂)_(b) --CONH--, ##STR386## n is 0, 1 or 2, and A₁ ' is asdefined above, each R₂₆ is independently hydrogen, halo, nitro, amino,C₁₋₄ alkyl, C₁₋₄ alkoxy, cyano, trifluoromethyl, phenyl, anilino,benzoyl, carbamoyl, phenoxy, halophenoxy, dihalophenoxy, C₁₋₄alkylsulfonyl, phenylsulfonyl, C₁₋₄ alkylsulfonylamino or N,N-di(C₁₋₄alkyl)sulfamoyl, each R₂₈ is independently hydrogen, halo, C₁₋₄ alkyl orC₁₋₄ alkoxy, and X is a direct bond, linear or branched ##STR387##wherein R₄₂ is halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, each R₄₃ isindependently linear or branched C₁₋₄ alkylene, each R₄₄ isindependently hydrogen or C₁₋₄ alkyl, R₄₅ is halo, hydroxy, methoxy,ethoxy, amino, 2-hydroxyethylamino, N,N-di-(2-hydroxyethyl)amino,--NH--(CH₂)_(b) --N(C₂ H₅)₂, N-methyl-N-phenylamino,N-cyclohexyl-N-methylamino or piperidino, and each g is independently 1,2, 3 or 4,wherein each B' is independently hydrogen, methyl, ethyl,hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂, --(CH₂)_(b)--N.sup.⊖ (R₈ ')₂ R₉ 'A.sup.⊖ or --A'--NH--R₂ ', wherein A' is linear orbranched C₂₋₈ alkylene or phenylene, R₂ ' is ##STR388## wherein R₁₁ ' ishydrogen, chloro, nitro, methyl or methoxy, R₁₂ ' is ##STR389## whereinR₁₃ ' is chloro, hydroxy, amino, N,N-di-(C₂₋₄ hydroxyalkyl)amino,##STR390## wherein R₁₁ ' is as defined above, R₁₄ ' is ##STR391## Z' is--N(R₇ ')₂ or --N(R₈ ')₂ R₉ 'A.sup.⊖, wherein R₇ ', R₈ ' and R₉ ' are asdefined below, and t is 1 or 2, each R₇ ' is independently hydrogen,C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl or --N(R₇ ')₂is pyrrolidino, piperidino, morpholino, piperazino orN'-methylpiperazino, each R₈ ' is independently C₁₋₆ alkyl,n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl, and R₉ ' is methyl,ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ ' is pyridinium,pyridinium substituted by 1 or 2 methyl groups or ##STR392## wherein Zois a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂ --, --NH--,--NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖, and R₉ ' is as definedabove,wherein R₅ ' is hydrogen, methyl or ethyl, and R₂₁ is C₁₋₁₂ alkyl;C₂₋₁₂ alkyl substituted by hydroxy; C₃₋₁₂ alkyl interrupted by 1 to 3radicals selected from ##STR393## wherein R₂₃ is halo, hydroxy, nitro,C₁₋₄ alkyl or C₁₋₄ alkoxy, R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉'A.sup.⊖, --CO--Y₂ --Z', --NHCO--Y₂ --Z', --CONH--Y₂ --Z'--SO₂ NH--Y₂--Z', --Y₂ --Z' or --NHNHCO--CH₂ --Z',wherein each R₅ ', R₇ ', R₈ ', R₉', R₁₃ ', R₁₄ ' and Z' is independently as defined above, each R_(5a) isindependently hydrogen or C₁₋₄ alkyl, each R₆ is independently C₁₋₄alkyl, each Y₁ is independently linear or branched C₁₋₈ alkylene orlinear or branched C₃₋₈ alkenylene, each Y₂ is independently linear orbranched C₁₋₈ alkylene, each a is independently 1, 2 or 3, each b isindependently 2 or 3, each m is independently 1, 2, 3, 4, 5 or 6, each qis independently 0 or 1, and each A.sup.⊖ is independently anon-chromphoric anion.
 7. A process according to claim 6 wherein the dyeis a metal-free compound of the formula ##STR394## or a 1:1 or 1:2 metalcomplex thereof, or an acid addition salt of a metal-free compound ofsaid formula or a 1:1 or 1:2 metal complex thereof,wherein B₁ ' ishydrogen, methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_(b)--N(R₇ ")₂ or --(CH₂)_(b) --N.sup.⊕ (Rhd 8")₂ R₉ "A.sup.⊖, wherein eachR₇ " is independently hydrogen, methyl, ethyl or 2-hydroxyethyl or--N(R₇ ")₂ is morpholino, piperidino, piperazino or N'-methylpiperazino,each R₈ " is independently methyl, ethyl or 2-hydroxyethyl, and R₉ " ismethyl, ethyl or benzyl or --N.sup.⊕ (R₈ ")₂ R₉ " is pyridinium,pyridinium substituted by 1 or 2 methyl groups or ##STR395## with theproviso that the number of basic and cationic groups exceeds the numberof sulfo groups by at least one.
 8. A process according to claim 7wherein the dye is a metal-free compound of the formula ##STR396## or anacid addition salt thereof.
 9. A process according to claim 6 whereinthe dye is a metal-free compound of the formula ##STR397## or a 1:1 or1:2 metal complex thereof, or an acid addition salt of a metal-freecompound of said formula or a 1:1 or 1:2 metal complex thereof,whereinA₁ " is ##STR398## wherein R₅₂ ' is hydrogen, chloro, hydroxy, methyl ormethoxy, each R₅₃ ' is independently hydrogen, chloro, methyl, methoxyor hydroxy, and Y_(o) ' is a direct bond, --NHCO-- or --NHCONH--, B₁ "is hydrogen, methyl, ethyl, benzyl, --(CH₂)_(b) --N(R₇ ")₂ or--(CH₂)_(b) --N.sup.⊕ (R₈ ")₂ R₉ "A.sup.⊖, R" is methyl or phenyl, R₁₇ "is hydrogen, ##STR399## wherein K₁ " is ##STR400## wherein K_(b) ' is##STR401## R₂₀ " is --NR₅ "--Q₁ --N(R₇ ")₂ or --NR₅ "--Q₁ --N.sup.⊕ (R₈")₂ R₉ "A.sup.⊖,wherein Q₁ is linear or branched C₂₋₆ alkylene, --CH₂C*O-- or --CH₂ --CON*H--, wherein the * denotes the atom attached to the--NR₅ -- radical, X_(o) " is --NH--, --NHCO--CH═CH--CONH-- or--NHCO--CH₂ CH₂ --CONH--, and A₁ " is as defined above, T" is cyano or##STR402## wherein R₃ " is hydrogen or methyl, wherein each R₂₈ isindependently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy R₂₉ ' is##STR403## wherein R₄₆ ' is hydrogen ##STR404## each R₄₇ ' isindependently hydrogen, chloro, bromo, methyl, ethyl, methoxy, ethoxy,nitro or cyano, and R₄₈ ' is methoxy or ethoxy, each R₃₃ ' isindependently hydrogen, 2-hydroxyethyl, 3-methoxypropyl, --(CH₂)_(b)--N(CH₃)₂ or --(CH₂)_(b) --N.sup.⊕ (CH₃)₃ A.sup.⊖, R₃₄ is hydroxy oramino, R₃₆ ' is hydrogen, ##STR405## wherein R₄₉ ' is hydrogen,##STR406## each R₅₀ ' is independently hydrogen, chloro, methyl ormethoxy, R₃₇ ' is ##STR407## R₃₈ ' is methyl, ethyl, 2-cyanomethyl orbenzyl, R₃₉ ' is methyl, ethyl or --(CH₂)_(m) '--Z, each R₄₀ isindependently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, and R₆₃ ' ishydrogen, methoxy, hydroxy, methyl or chloro,wherein each R₁₃ " isindependently --NR₅ "R₂₁ ', ##STR408## each R₁₄ " is independently --NR₅"R₂₁ ', ##STR409## wherein R₂₁ ' is ##STR410## wherein R₆ ' is methyl orethyl, Y₂ ' is linear or branched C₁₋₄ alkylene, and Z" is --N(R₇ ")₂ or--N.sup.⊕ (R₈ ")₂ R₉ " A.sup.⊖,wherein each R₅ " is independentlyhydrogen or methyl, each R₇ " is independently hydrogen, methyl, ethylor 2-hydroxyethyl or --N(R₇ ")₂ is morpholino, piperidino, piperazino orN'-methylpiperazino, each R₈ " is independently methyl, ethyl or2-hydroxyethyl, and each R₉ " is independently methyl, ethyl or benzylor --N.sup.⊕ (R₈ ")₂ R₉ " is pyridinium, pyridinium substituted by 1 or2 methyl groups or ##STR411## wherein each b is independently 2 or 3,each m' is independently 2, 3 or 4, each q is independently 0 or 1, andeach A.sup.⊖ is independently a non-chromophoric anion,with the provisothat the total number of basic and cationic groups exceeds the number ofsulfo groups by at least one.
 10. A process according to claim 9 whereinthe dye is a metal-free compound of the formula ##STR412## or an acidaddition salt thereof.
 11. A process according to claim 6 wherein thedye is a metal-free compound of the formula ##STR413## wherein each B"is independently hydrogen, 3-dimethylaminopropyl, ##STR414## each T₁ isindependently cyano or pyridinium A.sup.⊖, wherein A.sup.⊖ is anon-chromophoric anion, with the provisos that (i) the floating --N═N--radical on Ring A is in the 3'- or 4'-position thereof, (ii) thefloating --N═N-- radical on Ring B is in the 2- or 3-position thereof,and (iii) the total number of the basic and cationic groups is at leasttwo.
 12. A process to claim 1 wherein the dye is a metal-free compoundof the formula ##STR415## or a 1:1 or 1:2 metal complex thereof, or anacid addition salt of a metal-free compound of said formula or a 1:1 or1:2 metal complex thereof, wherein A₁ ' is ##STR416## wherein R₅₁ ishydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy,R₅₂ is hydrogen, hydroxy,halo, cyano, --CONH₂, (C₁₋₄ alkyl)carbonylamino, --NHCONH₂, carboxy,sulfo, C₁₋₄ alkyl or C₁₋₄ alkoxy, each R₅₃ is independently hydrogen,halo, cyano, C₁₋₄ alkyl, C₁₋₄ alkoxy, carboxy, sulfo or hydroxy, and Yois a direct bond, --(CH₂)_(a) --, --O--, --S--, --SO₂ --, --NHCO--,--NHCONH--, --NHCO--(CH₂)_(b) --CONH--, --CONH--(CH₂)_(b) --NHCO--,--O--(CH₂)_(b) --O--, --N═N-- or --CH═CH--CO--CH═CH--, B₁ ' is hydrogen,methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_(b) --N(R₇ ")₂or --(CH₂)_(b) --N.sup.⊕ (R₈ ")₂ R₉ " A.sup.⊖,wherein each R₇ " isindependently hydrogen, methyl, ethyl or 2-hydroxyethyl or --N(R₇ ")₂ ismorpholino, piperidino, piperazino or N'-methylpiperazino, each R₈ " isindependently methyl, ethyl or 2-hydroxyethyl, and R₉ " is methyl, ethylor benzyl or --N.sup.⊕ (R₈ ")₂ R₉ " is pyridinium, pyridiniumsubstituted by 1 or 2 methyl groups or ##STR417## wherein R₉ ' and Zoare as defined below, R' is methyl, ethyl, phenyl, benzyl or cyclohexyl,R_(17a) is ##STR418## wherein K₁ ' is ##STR419## wherein K_(b) is##STR420## wherein each R₂₈ is independently hydrogen, halo, C₁₋₄ alkylor C₁₋₄ alkoxy, R₂₉ is --(CH₂)_(m) --Z, ##STR421## wherein R₄₆ ishydrogen, ##STR422## each R₄₇ is independently hydrogen, halo, C₁₋₄alkyl, C₁₋₄ alkoxy, nitro or cyano, and R₄₈ is C₁₋₄ alkoxy, R₃₂ is C₁₋₄alkyl or phenyl, each R₃₃ is independently hydrogen, C₁₋₄ alkyl,--(CH₂)_(b) --OCH₃, 2-hydroxyethyl, --(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b)--N.sup.⊕ (CH₃)₃ A.sup.⊖, R₃₄ is amino or hydroxy, R₃₅ is C₁₋₄ alkyl,--COOR₆, --CO--N(R_(5a))₂ or --CONH--Y₁ --Z, R₃₆ is hydrogen, ##STR423##wherein R₄₉ is hydrogen, ##STR424## and each R₅₀ is independentlyhydrogen, halo, C₁₋₄ alkoxy, C₁₋₄ alkyl, nitro or amino, R₃₇ ishydrogen, ##STR425## R₃₈ is C₁₋₄ alkyl, benzyl or 2-cyanoethyl, R₃₉ isC₁₋₄ alkyl or --(CH₂)_(m) --Z, each R₄₀ is independently hydrogen, C₁₋₄alkyl or C₁₋₄ alkoxy, R₆₃ is hydrogen, chloro, nitro, C₁₋₄ alkyl, C₁₋₄alkoxy or hydroxy, R₆₄ is hydrogen, dimethylamino, trimethylammoniumA.sup.⊖, diethylamino, triethylammonium A.sup.⊖, ##STR426## R' is asdefined above, and B' and T' are as defined below, X_(o) ' is ##STR427##A₁ ' is as defined above, and T' is hydrogen, cyano, --CO--N(R₅ ')₂ or##STR428## wherein each R₃ ' is independently hydrogen, methyl, ethyl,amino or dimethylamino, and each R₅ ' is independently hydrogen, methylor ethyl,wherein B' is hydrogen, methyl, ethyl, hydroxyethyl,cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂, --(CH₂)_(b) --N.sup.⊕ (R₈')₂ R₉ ' A.sup.⊖ or --A'--NH--R₂ ', wherein A' is linear or branchedC₂₋₈ alkylene or phenylene, R₂ ' is ##STR429## wherein R₁₁ ' ishydrogen, chloro, nitro, methyl or methoxy, R₁₂ ' is --CO--(CH₂)_(t)--Z' or ##STR430## wherein R₁₃ ' is chloro, hydroxy, amino, N,N-di-(C₂₋₄hydroxyalkyl)amino ##STR431## wherein R₁₁ ' is as defined above, R₁₄ 'is ##STR432## Z' is --N(R₇ ')₂ or --N(R₈ ')₂ R₉ ' A.sup.⊖, wherein R₇ ',R₈ ' and R₉ ' are as defined below, and t is 1 or 2, each R₇ ' isindependently hydrogen, C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or2-cyanoethyl or --N(R₇ ')₂ is pyrrolidino, piperidino, morpholino,piperazino or N'-methylpiperazino, each R₈ ' is independently C₁₋₆alkyl, n-hydroxy-(C₂₋₃ alkyl), benzyl or 2-cyanoethyl, and R₉ ' ismethyl, ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ ' is pyridinium,pyridinium substituted by 1 or 2 methyl groups or ##STR433## wherein Zois a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂ --, --NH--,--NR₆ -- or --N.sup.⊕ (R₆)₂ -- A.sup.⊖, and R₉ ' is as definedabove,wherein R₅ ' is hydrogen, methyl or ethyl, and R₂₁ is C₁₋₁₂ alkyl;C₂₋₁₂ alkyl substituted by hydroxy; C₃₋₁₂ alkyl interrupted by 1 to 3radicals selected from ##STR434## wherein R₂₃ is halo, hydroxy, nitro,C₁₋₄ alkyl or C₁₋₄ alkoxy, R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, --CO--Y₂ --Z', --NHCO--Y₂ --Z', --CONH--Y₂ --Z' --SO₂ NH--Y₂--Z', --Y₂ --Z' or --NHNHCO--CH₂ --Z',wherein R₇ ', R₈ ' and R₉ ' are asdefined above, wherein each R_(5a) is independently hydrogen or C₁₋₄alkyl, each R₆ is independently C₁₋₄ alkyl, each R₁₃ ', R₁₄ ' and Z' isindependently as defined above, each Y₁ is independently linear orbranched C₁₋₈ alkylene or linear or branched C₃₋₈ alkenylene, each Y₂ isindependently linear or branched C₁₋₈ alkylene, each a is independently1, 2 or 3, each b is independently 2 or 3, each m is independently 1, 2,3, 4, 5 or 6, each q is independently 0 or 1, and each A.sup.⊖ isindependently a non-chromophoric anion,with the proviso that the totalnumber of basic and cationic groups exceeds the number of sulfo groupsby at least one.
 13. A process according to claim 6 wherein the dye is ametal-free compound of the formula ##STR435## or a 1:1 or 1:2 metalcomplex thereof, or an acid addition salt of a metal-free compound ofsaid formula or a 1:1 or 1:2 metal complex thereof, wherein R₁ " is--N═N--D', with the provisos that (i) when the compound is a monoazocompound free of sulfo groups, it contains at least onewater-solubilizing basic or cationic group, (ii) when the compound isfree of sulfo groups and is other than a monoazo compound, it containsat least two water-solubilizing groups, and (iii) when the compoundcontains one or more sulfo groups, the total number of basic andcationic groups exceeds the number of sulfo groups by at least one. 14.A process according to claim 13 wherein the dye is a metal-free compoundof the formula ##STR436## or an acid addition salt thereof.
 15. Aprocess according to claim 14 wherein D' is ##STR437##
 16. A processaccording to claim 1 wherein the dye is a metal-free compound of theformula ##STR438## or a 1:1 or 1:2 metal complex thereof, or an acidaddition salt of a metal-free compound of said formula or a 1:1 or 1:2metal complex thereof, whereinA" is 1,2-ethylene, 1,3-propylene,1,3-phenylene or 1,4-phenylene, R" is methyl or phenyl, R₁ '" is--N═N--D",wherein D" is ##STR439## wherein K_(a) " is ##STR440## R₁₇ 'is hydrogen, ##STR441## wherein R₂₀ ' is ##STR442## R₂ " is ##STR443##wherein R₁₂ " is ##STR444## wherein R₁₃ " is ##STR445## R₁₄ " is##STR446## Z" is --N(R₇ ")₂ or --N.sup.⊕ (R₈ ")₂ R₉ " A.sup.⊖, and T" iscyano or ##STR447## wherein R₃ " is hydrogen or methyl, wherein each A₁' is independently ##STR448## wherein R₅₁ is hydrogen, halo, C₁₋₄ alkylor C₁₋₄ alkoxy, R₅₂ is hydrogen, hydroxy, halo, cyano, --CONH₂, (C₁₋₄alkyl)carbonylamino, --NHCONH₂, carboxy, sulfo, C₁₋₄ alkyl or C₁₋₄alkoxy, each R₅₃ is independently hydrogen, halo, cyano, C₁₋₄ alkyl,C₁₋₄ alkoxy, carboxy, sulfo or hydroxy, and Yo is a direct bond,--(CH₂)_(a) --, --O--, --S--, --SO₂ --, --NHCO--, --NHCONH--,--NHCO--(CH₂)_(b) --CONH--, --CONH--(CH₂)_(b) --NHCO--, --O--(CH₂)_(b)--O--, --N═N-- or --CH═CH--CO--CH═CH--,wherein B' is hydrogen, methyl,ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂,--(CH₂)_(b) --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖ or --A'--NH--R₂ ', wherein A'is linear or branched C₂₋₈ alkylene or phenylene, R₂ ' is ##STR449##wherein R₁₁ ' is hydrogen, chloro, nitro, methyl or methoxy, R₁₂ ' is##STR450## wherein R₁₃ ' is chloro, hydroxy, amino, N,N-di-(C₂₋₄-hydroxyalkyl)amino, ##STR451## wherein R₁₁ ' is as defined above, R₁₄ 'is --NR₅ 'R₂₁, ##STR452## Z' is --N(R₇ ')₂ or --N.sup.⊕ (R₈ ')₂ R₉'A.sup.⊖, wherein R₇ ', R₈ ' and R₉ ' are as defined below, and t is 1or 2,wherein K₁ ' is ##STR453## wherein K_(b) is ##STR454## wherein R₂₉is --(CH₂)_(m) --Z, ##STR455## wherein R₄₆ is hydrogen, ##STR456## eachR₄₇ is independently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro orcyano, and R₄₈ is C₁₋₄ alkoxy, R₃₂ is C₁₋₄ alkyl or phenyl, each R₃₃ isindependently hydrogen, C₁₋₄ alkyl, --(CH₂)_(b) --OCH₃, 2-hydroxyethyl,--(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b) --N.sup.⊕ (CH₃)₃ A.sup.⊖, R₃₄ isamino or hydroxy, R₃₅ is C₁₋₄ alkyl, --COOR₆, --CO--N(R_(5a))₂ or--CONH--Y₁ --Z, R₃₆ is hydrogen, ##STR457## wherein R₄₉ is hydrogen,##STR458## and each R₅₀ is independently hydrogen, halo, C₁₋₄ alkoxy,C₁₋₄ alkyl, nitro or amino, R₃₇ is hydrogen, ##STR459## R₃₈ is C₁₋₄alkyl, benzyl or 2-cyanoethyl, R₃₉ is C₁₋₄ alkyl or --(CH₂)_(m) --Z,each R₄₀ is independently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₆₃ ishydrogen, chloro, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy or hydroxy, R₆₄ ishydrogen, dimethylamino, trimethylammonium A.sup.⊖, diethylamino,triethylammonium A.sup.⊖, ##STR460## and B' is as defined above, K_(b) 'is ##STR461## wherein B' is as defined above, each R' is independentlymethyl, ethyl, phenyl, benzyl or cyclohexyl, each R_(5a) isindependently hydrogen or C₁₋₄ alkyl, each R₅ ' is independentlyhydrogen, methyl or ethyl, each R₅ " is independently hydrogen ormethyl, each R₆ is independently C₁₋₄ alkyl, each R₇ ' is independentlyhydrogen, C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl or--N(R₇ ')₂ is pyrrolidino, piperidino, morpholino, piperazino orN'-methylpiperazino, each R₇ " is independently hydrogen, methyl, ethylor 2-hydroxyethyl or --N(R₇ ")₂ is morpholino, piperidino, piperazino orN'-methylpiperazino, each R₈ ' is independently C₁₋₆ alkyl,n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl, and each R₉ ' isindependently methyl, ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ 'is pyridinium, pyridinium substituted by 1 or 2 methyl groups or##STR462## wherein Zo is a direct bond, --CH₂ --, --O--, --S--, --SO--,--SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖, wherein R₆ isas defined above, and R₉ ' is as defined above, each R₈ " isindependently methyl, ethyl or 2-hydroxyethyl, and each R₉ " isindependently methyl, ethyl or benzyl or --N.sup.⊕ (R₈ ")₂ R₉ " ispyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR463##wherein R₉ ' and Zo are as defined above, each R₁₃ ' and R₁₄ ' isindependently as defined above, R₂₁ is C₁₋₁₂ alkyl; C₂₋₁₂ alkylsubstituted by hydroxy; C₃₋₁₂ alkyl interrupted by 1 to 3 radicalsselected from ##STR464## wherein R₂₃ is halo, hydroxy, nitro, C₁₋₄ alkylor C₁₋₄ alkoxy, R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖,--CO--Y₂ --Z', --NHCO--Y₂ --Z', --CONH--Y₂ --Z' --SO₂ NH--Y₂ --Z', --Y₂--Z' or --NHNHCO--CH₂ --Z',wherein R₇ ', R₈ ' and R₉ ' are as definedabove, and R_(5a) and R₆ are as defined above, R₂₁ ' is ##STR465##wherein R₆ ' is methyl or ethyl, Y₂ ' is linear or branched C₁₋₄alkylene, and R₇ ", R₈ ", R₂₄ and Z" are as defined above, each R₂₆ isindependently hydrogen, halo, nitro, amino, C₁₋₄ alkyl, C₁₋₄ alkoxy,cyano, trifluoromethyl, phenyl, anilino, benzoyl, carbamoyl, phenoxy,halophenoxy, dihalophenoxy, C₁₋₄ alkylsulfonyl, phenylsulfonyl, C₁₋₄alkylsulfonylamino or N,N-di(C₁₋₄ alkyl)sulfamoyl, each R₂₈ isindependently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₂₉ ' is##STR466## wherein R₄₆ ' is hydrogen, ##STR467## wherein R₁₃ " and R₁₄ "are as defined above, each R₄₇ ' is independently hydrogen, chloro,bromo, methyl, ethyl, methoxy, ethoxy, nitro or cyano, and R₄₈ ' ismethoxy or ethoxy, and each R₃₃ ' is independently hydrogen,2-hydroxyethyl, 3-methoxypropyl, --(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b)--N.sup.⊕ (CH₃)₃ A.sup.⊖, R₃₄ is hydroxy or amino, R₃₆ ' is hydrogen,##STR468## wherein R₄₉ ' is hydrogen, ##STR469## wherein R₁₃ ' and R₁₄ 'are as defined above, and each R₅₀ ' is independently hydrogen, chloro,methyl or methoxy, R₃₇ ' is ##STR470## wherein R₁₃ " and R₁₄ " are asdefined above, R₃₈ ' is methyl, ethyl, 2-cyanoethyl or benzyl, R₃₉ ' ismethyl, ethyl or --(CH₂)_(m) '--Z, R₄₀ is independently hydrogen, C₁₋₄alkyl or C₁₋₄ alkoxy, each T' is independently hydrogen, cyano,##STR471## wherein each R₃ ' is independently hydrogen, methyl, ethyl,amino or dimethylamino, and R₅ ' is as defined above, X' is ##STR472##wherein R_(42a) is hydrogen, chloro, methyl or methoxy, each R₄₃ isindependently linear or branched C₁₋₄ alkylene, each R₄₄ isindependently hydrogen or C₁₋₄ alkyl, R₄₅ is halo, 2-hydroxyethylamino,N,N-di-(2-hydroxyethyl)amino, amino, hydroxy, --NH--(CH₂)_(b) --N(C₂H₅)₂, N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino, piperidino,methoxy or ethoxy, R_(45a) is chloro, 2-hydroxyethylamino, methoxy,ethoxy, hydroxy, amino, N,N-di-(2-hydroxyethyl)amino,3-diethylaminopropylamino, N-methyl-N-phenylamino,N-cyclohexyl-N-methylamino or piperidino, and g is 1, 2, 3 or 4, X_(o) 'is ##STR473## wherein R₁₃ ' is as defined above, each Y₁ isindependently linear or branched C₁₋₈ alkylene or linear or branchedC₃₋₈ alkenylene, each Y₂ is independently linear or branched C₁₋₈alkylene, each Z' is independently as defined above, each a isindependently 1, 2 or 3, each b is independently 2 or 3, each m isindependently 1, 2, 3, 4, 5 or 6, each m' is independently 2, 3 or 4,each n is independently 0, 1 or 2, each q is independently 0 or 1, andeach A is independently a non-chromophoric anion,with the provisos that(i) when the compound is a monoazo compound free of sulfo groups, itcontains at least one water-solubilizing basic or cationic group, (ii)when the compound is free of sulfo groups and is other than a monoazocompound, it contains at least two water-solubilizing groups, and (iii)when the compound contains one or more sulfo groups, the total number ofbasic and cationic groups exceeds the number of sulfo groups by at leastone.
 17. A process according to claim 16 wherein the dye is a metal-freecompound of the formula ##STR474## or an acid addition salt thereof. 18.A process according to claim 1 wherein the dye is a metal-free compoundof the formula ##STR475## or a 1:1 or 1:2 metal complex thereof, or anacid addition salt of a metal-free compound of said formula or an acidaddition salt thereof, whereinA" is 1,2-ethylene, 1,3-propylene,1,3-phenylene or 1,4-phenylene, R₁ ^(iv) is --N═N--D"',wherein D"' is##STR476## wherein R₂₆ ' is hydrogen, nitro, chloro, methyl, methoxy orchlorophenoxy, each R_(26a) is independently nitro, chloro, methyl ormethoxy, each R_(27a) is independently hydrogen, chloro, methyl ormethoxy, and R_(27b) is hydrogen, methyl or methoxy, R₂ " is ##STR477##wherein R₁₂ " is ##STR478## wherein R₁₃ " is ##STR479## R₁₄ " is##STR480## Z" is --N(R₇ ")₂ or --N.sup.⊕ (R₈ ")₂ R₉ "A.sup.⊖, and T" iscyano or ##STR481## wherein R₃ " is hydrogen or methyl, wherein A₁ ' is##STR482## wherein R₅₁ is hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₅₂is hydrogen, hydroxy, halo, cyano, --CONH₂, (C₁₋₄ alkyl)carbonylamino,--NHCONH₂, carboxy, sulfo, C₁₋₄ alkyl or C₁₋₄ alkoxy, each R₅₃ isindependently hydrogen, halo, cyano, C₁₋₄ alkyl, C₁₋₄ alkoxy, carboxy,sulfo or hydroxy, and Yo is a direct bond, --(CH₂)_(a) --, --O--, --S--,--SO₂ --, --NHCO--, --NHCONH--, --NHCO--(CH₂)_(b) --CONH--,--CONH--(CH₂)_(b) --NHCO--, --O--(CH₂)_(b) --O--, --N═N-- or--CH═CH--CO--CH═CH--, K_(a) " is ##STR483## wherein K_(b) ' is##STR484## X", when both R_(27a) 's and R_(27b) are hydrogen, is adirect bond, ##STR485## wherein R_(42a) is hydrogen, chloro, methyl ormethoxy, R₄₃ is linear or branched C₁₋₄ alkylene, R_(45a) is chloro,2-hydroxyethylamino, methoxy, ethoxy, hydroxy, amino,N,N-di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino,N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino or piperidino, and gis 1, 2, 3 or 4, andwherein B' is hydrogen, methyl, ethyl, hydroxyethyl,cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂, --(CH₂)_(b) --N.sup.⊕ (R₈')₂ R₉ 'A.sup.⊕ or --A'--NH--R₂ ', wherein A' is linear or branched C₂₋₈alkylene or phenylene, R₂ ' is ##STR486## wherein R₁₁ ' is hydrogen,chloro, nitro, methyl or methoxy, and R₁₂ ' is ##STR487## wherein R₁₃ 'is chloro, hydroxy, amino, N,N-di-(C₂₋₄ -hydroxyalkyl)amino, ##STR488##wherein R₁₁ ' is as defined above, R₁₄ ' is ##STR489## and Z' is --N(R₇')₂ or --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, R' is methyl, ethyl, phenyl,benzyl or cyclohexyl, R₂₁ ' is ##STR490## wherein R₆ ' is methyl orethyl, R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, --CO--Y₂ --Z',--NHCO--Y₂ --Z', --CONH--Y₂ --Z' --SO₂ NH--Y₂ --Z', --Y₂ --Z' or--NHNHCO--CH₂ --Z',wherein Z' is as defined above, Y₂ ' is linear orbranched C₁₋₄ alkylene, and Z" is as defined above, each R₂₈ isindependently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₂₉ ' is##STR491## wherein R₄₆ ' is hydrogen, ##STR492## wherein R₁₃ ", R₁₄ "and Z' are as defined above, each R₄₇ ' is independently hydrogen,chloro, bromo, methyl, ethyl, methoxy, ethoxy, nitro or cyano, and R₄₈ 'is methoxy or ethoxy, and each R₃₃ ' is independently hydrogen,2-hydroxyethyl, 3-methoxypropyl, --(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b)--N.sup.⊕ (CH₃)₃ A.sup.⊖, R₃₄ is hydroxy or amino, R₃₆ ' is hydrogen,##STR493## wherein R₄₉ ' is hydrogen, ##STR494## wherein R₁₃ ', R₁₄ 'and Z' are as defined above, and each R₅₀ ' is independently hydrogen,chloro, methyl or methoxy, R₃₇ ' is ##STR495## wherein R₁₃ " and R₁₄ "are as defined above, R₃₈ ' is methyl, ethyl, 2-cyanoethyl or benzyl,R₃₉ ' is methyl, ethyl or --(CH₂)_(m) '--Z, R₄₀ is independentlyhydrogen, C₁₋₄ alkyl or C₁₋₄ -alkoxy, and each T' is independentlyhydrogen, cyano, ##STR496## wherein each R₃ ' is independently hydrogen,methyl, ethyl, amino or dimethylamino,wherein each R₇ ' is independentlyhydrogen, C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl or--N(R₇ ')₂ is pyrrolidino, piperidino, morpholino, piperazino orN'-methylpiperazino, each R₇ " is independently hydrogen, methyl, ethylor 2-hydroxyethyl or --N(R₇ ")₂ is morpholino, piperidino, piperazino orN'-methylpiperazino, each R₈ ' is independently C₁₋₆ alkyl,n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl, and each R₉ ' isindependently methyl, ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ 'is pyridinium, pyridinium substituted by 1 or 2 methyl groups or##STR497## wherein Zo is a direct bond, --CH₂ --, --O--, --S--, --SO--,--SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖, and R₉ ' is asdefined above, each R₈ " is independently methyl, ethyl or2-hydroxyethyl, and each R₉ " is independently methyl, ethyl or benzylor --N.sup.⊕ (R₈ ")₂ R₉ " is pyridinium, pyridinium substituted by 1 or2 methyl groups or ##STR498## wherein R₉ ' and Zo are as defined above,each R₁₃ ' and R₁₄ ' is independently as defined above, R₂₁ is C₁₋₁₂alkyl; C₂₋₁₂ alkyl substituted by hydroxy; C₃₋₁₂ alkyl interrupted by 1to 3 radicals selected from ##STR499## wherein R₂₃ is halo, hydroxy,nitro, C₁₋₄ alkyl or C₁₋₄ alkoxy, and R₂₄ and Z' are as definedabove,wherein each R₅ ' is independently hydrogen, methyl or ethyl, eachR₅ " is independently hydrogen or methyl, each R_(5a) is independentlyhydrogen or C₁₋₄ alkyl, each R₆ is independently C₁₋₄ alkyl, each Y₁ isindependently linear or branched C₁₋₈ alkylene or linear or branchedC₃₋₈ alkenylene, each Y₂ is independently linear or branched C₁₋₈alkylene, each a is independently 1, 2 or 3, each b is independently 2or 3, each m' is independently 2, 3 or 4, each n is independently 0, 1or 2, each q is independently 0 or 1, each t is independently 1 or 2,and each A.sup.⊖ is independently a non-chromophoric anion,with theprovisos that (i) when the compound is a monoazo compound free of sulfogroups, it contains at least one water-solubilizing basic or cationicgroup, (ii) when the compound is free of sulfo groups and is other thana monoazo compound, it contains at least two water-solubilizing groups,and (iii) when the compound contains one or more sulfo groups, the totalnumber of basic and cationic groups exceeds the number of sulfo groupsby at least one.
 19. A process according to claim 18 wherein the dye isa metal-free compound of the formula ##STR500## or an acid addition saltthereof.
 20. A process according to claim 1 wherein the dye is ametal-free compound of the formula ##STR501## or a 1:1 or 1:2 metalcomplex thereof, or an acid addition salt of a metal-free compound ofsaid formula or a 1:1 or 1:2 metal complex thereof, wherein oneR₆₀ ishydroxy and the other is amino, R₆₁ is hydrogen, C₁₋₄ alkoxy or hydroxy,R₆₂ is hydrogen, chloro, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy or hydroxy, R₆₃is hydrogen, chloro, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy or hydroxy, R₆₄ ishydrogen, dimethylamino, trimethylammonium A.sup.⊖, diethylamino,triethylammonium A.sup.⊖, ##STR502## wherein Y₂ is linear or branchedC₁₋₈ alkylene, each M is independently hydrogen or a non-chromophoriccation,with the provisos that (i) the total number of cationic andprotonatable basic groups exceeds the number of sulfo groups by at leastone, and (ii) R₆₄ is the 3- or 4-position of the ring to which it isattached.
 21. The process according to claim 20 wherein the dye is ametal-free compound of the formula ##STR503## or acid addition saltthereof.
 22. A process according to claim 1 wherein the dye is a 1:1 or1:2 metal complex of the formula ##STR504## or an acid addition saltthereof, wherein B' is hydrogen, methyl, ethyl, hydroxyethyl,cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂, --(CH₂)_(b) --N.sup.⊕ (R₈')₂ R₉ 'A.sup.⊖ or --A'--NH--R₂ ',wherein A' is linear or branched C₂₋₈alkylene or phenylene, R₂ ' is ##STR505## wherein R₁₁ ' is hydrogen,chloro, nitro, methyl or methoxy, R₁₂ ' is ##STR506## wherein R₁₃ ' ischloro, hydroxy, amino, N,N-di-(C₂₋₄ -hydroxyalkyl)amino, ##STR507##wherein R₁₁ ' is as defined above, R₁₄ ' is ##STR508## Z' is --N(R₇ ')₂or --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, wherein R₇ ', R₈ ' and R₉ ' are asdefined below, and t is 1 or 2, each R₇ ' is independently hydrogen,C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl or --N(R₇ ')₂is pyrrolidino, piperidino, morpholino, piperazino orN'-methylpiperazino, each R₈ ' is independently C₁₋₆ alkyl,n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl, and R₉ ' is methyl,ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ ' is pyridinium,pyridinium substituted by 1 or 2 methyl groups or ##STR509## wherein Zois a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂ --, --NH--,--NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖, and R₉ ' is as definedabove,wherein R₅ ' is hydrogen, methyl or ethyl, and R₂₁ is C₁₋₁₂ alkyl;C₂₋₁₂ alkyl substituted by hydroxy; C₃₋₁₂ alkyl interrupted by 1 to 3radicals selected from ##STR510## wherein R₂₃ is halo, hydroxy, nitro,C₁₋₄ alkyl or C₁₋₄ alkoxy, R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉'A.sup.⊖, --CO--Y₂ --Z', --NHCO--Y₂ --Z', --CONH--Y₂ --Z'--SO₂ NH--Y₂--Z', --Y₂ --Z' or --NHNHCO--CH₂ --Z',wherein R₇ ', R₈ ' and R₉ ' are asdefined above, K_(a) ' is ##STR511## wherein K_(b) is ##STR512## whereineach R₂₈ is independently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₂₉is --(CH₂)_(m) --Z, ##STR513## wherein R₄₆ is hydrogen, ##STR514## eachR₄₇ is independently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro orcyano, and R₄₈ is C₁₋₄ alkoxy, R₃₂ is C₁₋₄ alkyl or phenyl, each R₃₃ isindependently hydrogen, C₁₋₄ alkyl, --(CH₂)_(b) --OCH₃, 2-hydroxyethyl,--(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b) --N.sup.⊕ (CH₃)₃ A.sup.⊖, R₃₄ isamino or hydroxy, R₃₅ is C₁₋₄ alkyl, --COOR₆, --CO--N(R_(5a))₂ or--CONH--Y₁ --Z, R₃₆ is hydrogen, ##STR515## wherein R₄₉ is hydrogen,##STR516## and each R₅₀ is independently hydrogen, halo, C₁₋₄ alkoxy,C₁₋₄ alkyl, nitro or amino, R₃₇ is hydrogen, --NHCO--(CH₂)_(a) --Z,--SO₂ NH--Y₁ --Z, --CONH--Y₁ --Z, --CONHNH₂, --NH--Y₁ --Z, --CH₂ --Z,--NHNHCO--CH₂ --Z, nitrophenylcarbamoyl or ##STR517## R₃₈ is C₁₋₄ alkyl,benzyl or 2-cyanoethyl, R₃₉ is C₁₋₄ alkyl or --(CH₂)_(m) --Z, each R₄₀is independently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, B' is as definedabove, and R' and T' are as defined below, R' is methyl, ethyl, phenyl,benzyl or cyclohexyl, each R₅₁ is independently hydrogen, halo, C₁₋₄alkyl or C₁₋₄ alkoxy, each R₅₂ is independently hydrogen, halo, C₁₋₄alkyl, C₁₋₄ alkoxy, hydroxy, cyano, carbamoyl, (C₁₋₄alkyl)carbonylamino, ureido, carboxy or sulfo, one R₆₀ is hydroxy andthe other is amino, R_(60b) is hydroxy when Y_(a) is --NH-- and is aminowhen Y_(a) is --O--, R₆₂ ' is hydrogen, chloro or methyl, R₆₃ ' ishydrogen, chloro, methyl, methoxy or hydroxy, R₆₄ is hydrogen,dimethylamino, trimethylammonium A.sup.⊖, diethylamino, triethylammoniumA.sup.⊖, ##STR518## T' is hydrogen, cyano, --CO--N(R₅ ')₂ or ##STR519##wherein each R₃ ' is independently hydrogen, methyl, ethyl, amino ordimethylamino, and each R₅ ' is independently hydrogen, methyl or ethyl,X is a direct bond, linear or branched C₁₋₄ alkylene, ##STR520## whereinR₄₂ is halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, each R₄₃ is independently linearor branched C₁₋₄ alkylene, each R₄₄ is independently hydrogen or C₁₋₄alkyl, R₄₅ is halo, hydroxy, methoxy, ethoxy, amino,2-hydroxyethylamino, N,N-di-(2-hydroxyethyl)amino, --NH--(CH₂)_(b)--N(C₂ H₅)₂, N--methyl--N--phenylamino, N-cyclohexyl-N-methylamino orpiperidino, and each g is independently 1, 2, 3 or 4, Y_(a) is --O-- or--NH--, each Me independently is copper, chromium, cobalt, nickel, iron,manganese or zinc when the complex is a 1:1 metal complex and ischromium, cobalt, iron or nickel when the complex is a 1:2 metalcomplex, and each M is independently hydrogen or a non-chromophoriccation,wherein each R_(5a) is independently hydrogen or C₁₋₄ alkyl, eachR₆ is independently C₁₋₄ alkyl, each R₁₃ ', R₁₄ ' and Z' isindependently as defined above, each Y₁ is independently linear orbranched C₁₋₈ alkylene or linear or branched C₃₋₈ alkenylene, each Y₂ isindependently linear or branched C₁₋₈ alkylene, each a is independently1, 2 or 3, each b is independently 2 or 3, each m is independently 1, 2,3, 4, 5 or 6, each n is independently 0, 1 or 2, each q is independently0 or 1, and each A.sup.⊖ is independently a non-chromophoric anion,withthe provisos that (i) when the complex is a complex of a metal-free azocompound free of sulfo groups, the metal-free azo compound contains atleast two water-solubilizing groups, (ii) when the complex is a complexof a metal-free azo compound containing one or more sulfo groups, thetotal number of basic and cationic groups of the metal-free azo compoundexceeds its number of sulfo groups by at least one, (iii) R₆₄ is in the3- or 4-position of the ring to which it is attached, (iv) the floatingazo radical on Ring G is in the 3- or 4-position thereof, and (v) thefloating --O--Me--Y_(a) -- radical and the floating azo radical on RingG in each complex of Formula IVh are ortho to each other.
 23. Asubstrate dyed or printed with a metal-free compound of the formula##STR521## or a 1:1 or 1:2 metal complex thereof, or an acid additionsalt of a metal-free compound of said formula or a 1:1 or 1:2 metalcomplex thereof, wherein B is hydrogen; C₁₋₄ alkyl C₁₋₄ alkylmonosubstituted by C₁₋₄ alkoxy; C₂₋₄ alkyl substituted by hydroxy; C₅₋₆cycloalkyl; C₅₋₆ cycloalkyl substituted by 1 to 3 C₁₋₄ alkyl groups;phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenyl group of which issubstituted by 1 to 3 substituents selected from C₁₋₄ alkyl, C₁₋₄ alkoxyand halo; --A--NH--R₂ ; --A₄ '--N(R₇)₂ ; --A₄ --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖or --N(R₇)₂,wherein A is linear or branched C₂₋₈ alkylene; linear orbranched C₂₋₈ alkylene interrupted by 1 or 2 hetero atoms; linear orbranched C₂₋₈ alkenylene; linear or branched C₂₋₈ alkenylene interruptedby 1 or 2 hetero atoms; phenylene or cyclohexylene, A₄ is linear orbranched C₂₋₈ alkylene or linear or branched C₂₋₈ alkenylene, A₄ ' islinear or branched C₁₋₈ alkylene or linear or branched C₂₋₈ alkenylene,and R₂ is ##STR522## wherein R₁₁ is hydrogen, halo, nitro, C₁₋₄ alkyl orC₁₋₄ alkoxy, and R₁₂ is ##STR523## wherein Z is --N(R₇)₂ or --N.sup.⊕(R₈)₂ R₉ A.sup.⊖, and a is 1, 2 or 3, R is hydrogen; C₁₋₄ alkyl; C₅₋₆cycloalkyl; C₅₋₆ cycloalkyl substituted by 1 or 2 C₁₋₄ alkyl groups;phenyl; phenyl substituted by 1 or 2 substituents selected from methyl,ethyl, methoxy and ethoxy; benzyl; phenylethyl; or benzyl or phenylethylthe phenyl group of which is substituted by 1 or 2 substituents selectedfrom methyl, ethyl, methoxy and ethoxy, R₁ is --N═N--D,wherein D is adiazo component radical, with the proviso that R₁ must be ##STR524##when B is other than --A--NH--R₂, wherein A₁ is a tetrazo componentradical, R₁₇ is hydrogen, ##STR525## wherein A₁₀ is a tetrazo componentradical or a coupling/diazo component radical, K₁ is a diazo componentradical or a coupling component radical, R₂₀ is ##STR526## wherein Q₁ islinear or branched C₂₋₆ alkylene, --CH₂ C*O-- or --CH₂ --CON*H--,wherein the * denotes the atom attached to the --(NR₅)_(q) -- radical,and Q₂ is linear or branched C₂₋₆ alkylene, --CH₂ C*O--, --CH₂ CON*H--or --CH₂ CONHC*O--, wherein the * denotes the atom attached to the--(NR₅)_(q) -- radical, X_(o) is a bridging radical, R₁₉ is hydrogen;hydroxy; amino; (C₁₋₄ alkyl)carbonylamino; benzoylamino; phenylamino; orbenzoylamino or phenylamino the phenyl group of which is substituted by1 or 2 substituents selected from halo, nitro, amino, C₁₋₄ alkyl andC₁₋₄ alkoxy, with the proviso that R₁₉ must be hydrogen when R₁₇ isother than --N═N--K₁ and --N═N--A₁₀ --N═N--K₁, and R₆₀ is hydroxy oramino, and R_(60a) is hydrogen, hydroxy or amino, with the proviso thatR_(60a) is hydrogen or amino when R₆₀ is hydroxy and is hydroxy when R₆₀is amino, and T is hydrogen, cyano, --COOR₄, --CO--N(R₅)₂, --SO₂--N(R₅)₂, ##STR527## wherein each R₃ is independently hydrogen, C₁₋₄alkyl, --N(R₅)₂ or --CO--N(R₅)₂, R₄ is C₁₋₆ alkyl or phenyl(C₁₋₃ alkyl),R₆ is C₁₋₄ alkyl, and X_(a) is --O--, --NR₅ -- or --S--,wherein each R₅is independently hydrogen or C₁₋₄ alkyl or, when two R₅ 's are attachedto a nitrogen atom, both R₅ 's taken together and with the nitrogen atommay form a saturated ring containing 1 to 3 hetero atoms, each R₇ isindependently hydrogen; C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by halo,hydroxy or cyano; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenylgroup of which is substituted by 1 to 3 substituents selected from halo,C₁₋₄ alkyl and C₁₋₄ alkoxy; C₅₋₆ cycloalkyl or C₅₋₆ cycloalkylsubstituted by 1 or 3 C₁₋₄ alkyl groups, or both R₇ 's taken togetherand with the nitrogen atom to which they are attached form a 5- or6-membered saturated ring containing 1 to 3 hetero atoms, each R₈ isindependently C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by halo, hydroxy orcyano; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenyl group of whichis substituted by 1 to 3 substituents selected from halo, C₁₋₄ alkyl andC₁₋₄ alkoxy; C₅₋₆ cycloalkyl or C₅₋₆ cycloalkyl substituted by 1 or 3C₁₋₄ alkyl groups, each R₉ is independently C₁₋₄ alkyl or C₁₋₄ alkylsubstituted by phenyl or both R₈ 's and R₉ taken together and with thenitrogen atom to which they are attached are pyridinium; pyridiniumsubstituted by 1 or 2 C₁₋₄ alkyl groups; or a 5- or 6-membered saturatedring containing 1 to 3 hetero atoms, each R₁₃ is independently amino; analiphatic , cycloaliphatic, aromatic or heterocyclic amino group thenitrogen atom of which is attached to the 1,3,5-triazine ring; halo;hydroxy; C₁₋₄ alkoxy; phenyl or ##STR528## wherein A₂ is linear orbranched C₂₋₆ alkylene or --N*HCOCH₂ --, wherein the * denotes the atomattached to the --NR₅ -- radical, and R, R₁, R₅ and T are as definedabove, each R₁₄ is independently an aliphatic, cycloaliphatic, aromaticor heterocyclic amino group the nitrogen atom of which is attached tothe 1,3,5-triazine ring, each n is independently 0, 1 or 2, each q isindependently 0 or 1, and each A.sup.⊖ is independently anon-chromophoric anion, with the provisos that (i) when the compound ofFormula I is a monoazo compound free of sulfo groups, it contains atleast one water-solubilizing basic or cationic group, (ii) when thecompound of Formula I is free of sulfo groups and is other than amonoazo compound, it contains at least two water-solubilizing groups,and (iii) when the compound of Formula I contains one or more sulfogroups, the total number of basic and cationic groups exceeds the numberof sulfo groups by at least one, said substrate being a substratedyeable or printable therewith.
 24. A dyed or printed substrateaccording to claim 23 wherein the dyed or printed substrate is a fiber,thread or textile material comprising a natural or regeneratedcellulosic material or a homopolymer or copolymer of acrylonitrile or1,1-dicyanoethylene or is leather or paper.